Electrolyte separators including lithium borohydride and composite electrolyte separators of lithium-stuffed garnet and lithium borohydride

ABSTRACT

Set forth herein are compositions comprising A.(LiBH 4 ).B.(LiX).C.(LiNH 2 ), wherein X is fluorine, bromine, chloride, iodine, or a combination thereof, and wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 that are suitable for use as solid electrolyte separators in lithium electrochemical devices. Also set forth herein are methods of making A.(LiBH 4 ).B.(LiX).C.(LiNH 2 ) compositions. Also disclosed herein are electrochemical devices which incorporate A.(LiBH 4 ).B.(LiX).C.(LiNH 2 ) compositions and other materials.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a National Stage filing under 35 U.S.C. § 371 ofInternational Patent Application No. PCT/US2017/057735, filed Oct. 20,2017, which claims priority to and the benefit of U.S. provisionalapplication No. 62/411,464, filed on Oct. 21, 2016, which isincorporated by reference herein in its entirety for all purposes.

FIELD

Provided herein are novel Lithium Borohydridecompositions—A.(LiBH₄).B.(LiX).C.(LiNH₂); wherein X is F, Br, Cl, I or acombination thereof; and wherein 0.1≤A≤4, 0.1≤B≤5, and 0≤C≤9.5—suitablefor use as solid-state electrolyte separators in electrochemical cellsand devices. Also set forth herein are methods for making the same.

BACKGROUND OF THE INVENTION

In a rechargeable Li⁺ ion battery, Li⁺ ions move from a negativeelectrode to a positive electrode during discharge and in the oppositedirection during charge. This process produces electrical energy(Energy=Voltage×Current) in a circuit connecting the electrodes, whichis electrically insulated from, but parallel to, the Li⁺ ion conductionpath. The battery's voltage (V versus Li) is a function of the chemicalpotential difference for Li situated in the positive electrode ascompared to the negative electrode. The battery's voltage is maximizedwhen Li metal is used as the negative electrode. An electrolytephysically separates and electrically insulates the positive andnegative electrodes while also providing a conduction medium for Li⁺ions. The electrolyte ensures that when Li metal oxidizes at thenegative electrode during discharge (e.g., Li←Li⁺+e⁻) and produceselectrons, these electrons conduct between the electrodes by way of anexternal circuit which is not the same pathway taken by the Li⁺ ions.

Conventional rechargeable batteries use liquid electrolytes to conductlithium ions between and within the positive and negative electrodes.However, liquid electrolytes suffer from several problems includingflammability during thermal runaway, outgassing at high voltages, andchemical incompatibility with lithium metal negative electrodes. As analternative, solid electrolytes have been proposed for next generationrechargeable batteries. For example, Li⁺ ion-conducting ceramic oxides,such as lithium-stuffed garnets, have been considered as electrolyteseparators. See, for example, US Patent Application Publication No.2015/0099190, published Apr. 9, 2015, and filed Oct. 7, 2014, titledGARNET MATERIALS FOR LI SECONDARY BATTERIES AND METHODS OF MAKING ANDUSING GARNET MATERIALS; U.S. Pat. Nos. 8,658,317; 8,092,941; and7,901,658; also U.S. Patent Application Publication Nos. 2013/0085055;2011/0281175; 2014/0093785; and 2014/0170504; also Bonderer, et al.“Free-Standing Ultrathin Ceramic Foils,” Journal of the American CeramicSociety, 2010, 93, 3624-3631; and Murugan, et al., Angew Chem. Int. Ed.2007, 46, 7778-7781, the entire contents of each of these publicationsare incorporated by reference in their entirety for all purposes. Seealso, e.g., Maekawa, H. et al., Journal of the American Chemical Society2009, 131, 894-895; Matsu, M. et al., Chem. Mater. 2010, 22, 2702-2704;Zhou, Y. et al., Materials Transactions 2011, 52, 654; and Borgschulte.A. et al., Energy Environ. Sci. 2012, 5, 6823-6832, the entire contentsof each of these publications are incorporated by reference in theirentirety for all purposes.

Solid electrolytes tend to reduce a battery's total weight and volume,when compared to a liquid electrolyte, and thereby increase itsgravimetric and volumetric energy density. Despite these advantages,solid electrolytes are still insufficient in several regards forcommercial applications. Notably, solid electrolytes tend to includedefects, grain boundaries, pores, atomic vacancies, uneven or roughsurfaces, and other inhomogeneous, non-uniform features whichresearchers find correlate with the formation of Li-dendrites when theseelectrolytes are used in electrochemical cells. A challenge in the fieldhas been to modify and/or reduce the number of these defects.

There is therefore a need for improved materials and methods for makingsolid electrolytes with a reduced number of defects. What is needed are,for example, new separators, e.g., a thin film composites of alithium-stuffed garnet with a material which passivates sites on thelithium-stuffed garnet from forming lithium dendrites. The instantdisclosure provides solutions to some of these problems as well asothers problems in the relevant field.

SUMMARY

In one embodiment, disclosed herein is a composition includingA·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X is fluorine (F), bromine (Br),chloride (CO, iodine (I), or a combination thereof, and wherein 0.1≤A≤4,0.1≤B≤4, and 0≤C≤9.

In a second embodiment, disclosed herein is an electrochemical cell thatincludes a lithium metal negative electrode; a solid electrolyteseparator; and a positive electrode, wherein the solid electrolyteseparator is between and in direct contact with the lithium metalnegative electrode and the positive electrode; and wherein the solidseparator comprises a composition which includesA·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X is fluorine (F), bromine (Br),chloride (CO, iodine (I), or a combination thereof, and wherein0.1<≤A≤4, 0.1≤B≤5, and 0≤C≤9.5.

In a third embodiment, disclosed herein is a method for making a thinfilm including (a) providing a powder mixture, wherein the powdermixture includes A·(LiBH₄)·B·(LiX)·C·(LiNH₂); wherein X is F, Br, Cl, Ior a combination thereof; and wherein 0.1≤A≤4, 0.1≤B≤5, and 0≤C≤9.5; (b)dropping, casting, or spraying the powder mixture on a substrate; (c)heating the powder mixture on a substrate to the powder mixture meltingpoint but lower than the powder mixture decomposition temperature; and(d) cooling the powder mixture on a substrate to room temperature.

In a fourth embodiment, disclosed herein is a method for making a thinfilm including (a) providing a powder mixture, wherein the powdermixture includes A·(LiBH₄)·B·(LiX)·C·(LiNH₂); wherein X is F, Br, Cl, Ior a combination thereof; and wherein 0.1≤A≤4, 0.1≤B≤5, and 0≤C≤9.5; (b)dropping, casting, or spraying the powder mixture onto a substrate; (c)heating the powder mixture on the substrate to above the powder mixturemelting point but below than the powder mixture decompositiontemperature; (c) spinning the powder mixture on a substrate; and (d)cooling the powder mixture on a substrate to room temperature.

In a fifth embodiment, disclosed herein is a method for making a thinfilm including (a) providing a powder mixture, wherein the powdermixture includes: A·(LiBH₄)·B·(LiX)·C·(LiNH₂); wherein X is F, Br, Cl, Ior a combination thereof; and wherein 0.1≤A≤4, 0.1≤B≤5, and 0≤C≤9.5; (b)mixing the powder mixture with a solvent to form a suspension; (c)dropping, casting, or spraying the suspension on a substrate; and (d)evaporating the solvent.

In a sixth embodiment, disclosed herein is a method for making a thinfilm including (a) providing a molten mixture, wherein the moltenmixture comprises: A·(LiBH₄)·B·(LiX)·C·(LiNH₂); wherein X is F, Br, Cl,I or a combination thereof; and wherein 0.1≤A≤4, 0.1≤B≤5, and 0≤C≤9.5;(b) dip-coating a substrate in the molten mixture, (c) withdrawing thesubstrate; and (d) cooling the substrate to room temperature.

In a seventh embodiment, disclosed herein is a method for making a thinfilm including (a) providing a molten mixture, wherein the powdermixture includes A·(LiBH₄)·B·(LiX)·C·(LiNH₂); wherein X is F, Br, Cl, Ior a combination thereof; an wherein 0.1≤A≤4, 0.1≤B≤5, and 0≤C≤9.5; (b)dip-coating a substrate in the molten mixture, (c) withdrawing thesubstrate; and (d) cooling the substrate.

In an eighth embodiment, disclosed herein is a method for making amultilayer component including (a) providing a first composition,wherein the composition includes A·(LiBH₄)·B·(LiX)·C·(LiNH₂); wherein Xis F, Br, Cl, I or a combination thereof; and wherein 0.1≤A≤4, 0.1≤B≤5,and 0≤C≤9.5; (b) dropping or spraying the powder mixture on a substrate;(c) heating the powder mixture on the substrate to above the powdermixture melting point but below than the powder mixture decompositiontemperature; (e) providing a layer of a second composition on top of thepowder mixture on a substrate to form a multilayer; (f) applying 1pound-per-square inch (PSI) to 1000 PSI pressure to the multilayer; and(f) cooling the powder mixture on a substrate to room temperature.

In a ninth embodiment, disclosed herein is a method for coating alithium-ion conducting separator electrolyte, the method including (a)providing a lithium-ion conducting separator electrolyte; and (b)pressing a composition of A·(LiBH₄)·B·(LiX)·C·(LiNH₂); wherein X isfluorine, bromine, chloride, iodine, or a combination thereof; andwherein 0.1≤A≤4, 0.1≤B≤5, and 0≤C≤9.5 on to at least one surface of thelithium-ion conducting separator electrolyte; wherein the pressing is ata temperature between 100-280° C. and at a pressure of 10-2000 PSI.

In a tenth embodiment, disclosed herein is a method for coating alithium-ion conducting electrolyte separator, the method including (a)providing a lithium-ion conducting electrolyte separator; (b) providinga mixture of a solvent and a composition of A·(LiBH₄)·B·(LiX)·C·(LiNH₂);wherein X is fluorine, bromine, chloride, iodine, or a combinationthereof; and wherein 0.1≤A≤4, 0.1≤B≤5, and 0≤C≤9.5; and (c) depositingthe mixture on the separator by spray coating, melt spin coating, spincoating, dip coating, slot die coating, gravure coating, or microgravurecoating.

In an eleventh embodiment, disclosed herein is a method for making athin film including a composition comprisingA·(LiBH₄)·B·(LiX)·C·(LiNH₂), wherein X is fluorine, bromine, chlorine,iodine, or a combination thereof, and wherein 0.1≤A≤4, 0.1≤B≤5, and0≤C≤9.5, the method including (a) providing a molten mixture, whereinthe mixture includes A·(LiBH₄)·B·(LiX)·C·(LiNH₂), wherein X is fluorine,bromine, chlorine, iodine, or a combination thereof, and wherein0.1≤A≤4, 0.1≤B≤5, and 0≤C≤9.5; (b) dip-coating a substrate in the moltenmixture; (c) withdrawing the substrate; and (d) cooling the substrate toroom temperature.

In a twelfth embodiment, disclosed herein is a method for coating alithium ion conducting separator electrolyte, the method including (a)providing a lithium ion conducting separator electrolyte; and (b)laminating a composition of A·(LiBH₄)·B·(LiX)·C·(LiNH₂), wherein X isfluorine, bromine, chlorine, iodine, or a combination thereof, to thelithium ion conducting separator electrolyte, and wherein 0.1≤A≤4,0.1≤B≤5, and 0≤C≤9.5 at a temperature between 100-280° C. at a pressureof 10-2000 pounds per square inch (PSI) on at least one surface of thelithium ion conducting separator electrolyte.

In thirteenth embodiment, disclosed herein is a method for coating alithium ion conducting separator electrolyte, the method including (a)providing a lithium ion conducting separator electrolyte; and (b)drop-casting a powder of a composition of A·(LiBH₄)·B·(LiX)·C·(LiNH₂),wherein X is fluorine, bromine, chlorine, iodine, or a combinationthereof, and wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 on at least one surfaceof the lithium ion conducting separator electrolyte; (c) heating thepowder on at least one surface of the lithium ion conducting separatorelectrolyte to a temperature between 100-280° C.; (d) optionallyremoving excessive material above a determined film thickness; and e)cooling the substrate to 100° C.

In fourteenth embodiment, disclosed herein is a method for coating asolid-state cathode film, the method including (a) providing asolid-state cathode film; and (b) drop-casting a powder of a compositionof A·(LiBH₄)·B (LiX)·C·(LiNH₂), wherein X is fluorine, bromine,chlorine, iodine, or a combination thereof, and wherein 0.1≤A≤3,0.1≤B≤4, and 0≤C≤9, on at least one surface of the solid-state cathode;(c) heating to a temperature between 100-280° C.; (d) optionallyremoving excessive material above a determined film thickness; and (e)cooling the substrate to 100° C.

In fifteenth embodiment, disclosed herein is a method to bonding alithium ion conducting separator electrolyte and a solid-state cathodeor another lithium ion conducting separator electrolyte with a moltencomposition of A·(LiBH₄)·B·(LiX)·C·(LiNH₂), wherein X is fluorine,bromine, chloride, iodine, or a combination thereof, and wherein0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9; wherein the method includes (a) providing afirst layer of a lithium ion conducting separator electrolyte; and (b)drop-casting a powder of a composition of A·(LiBH₄)·B·(LiX)·C·(LiNH₂),wherein X is fluorine, bromine, chlorine, iodine, or a combinationthereof, and wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9m on at least onesurface of the lithium ion conducting separator electrolyte; (c) heatingthe powder on at least one surface of the lithium ion conductingseparator electrolyte to a temperature between 100-280° C.; (d) placinga second layer on the first layer, wherein the second layer includes asolid-state cathode film or a lithium ion conducting separator; e)pressing the stack at a pressure of 10-2000 pounds per square inch(PSI); and f) cooling the stack to room temperature.

In sixteenth embodiment, disclosed herein is a method to bonding alithium ion conducting separator electrolyte and a solid-state cathodeor another lithium ion conducting separator electrolyte with a moltencomposition of A·(LiBH₄)·B·(LiX)·C·(LiNH₂), wherein X is fluorine,bromine, chloride, iodine, or a combination thereof, and wherein0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9; wherein the method includes (a) providing afirst lithium ion conducting separator electrolyte on a substrate; andb) drop-casting a powder of a composition ofA·(LiBH₄)·B·(LiX)·C·(LiNH₂), wherein X is fluorine, bromine, chlorine,iodine, or a combination thereof, and wherein 0.1≤A≤3, 0.1≤B≤4, and0≤C≤9 on at least one surface of the lithium ion conducting separatorelectrolyte; (c) heating the powder on at least one surface of thelithium ion conducting separator electrolyte to a temperature between100-280° C.; (d), rotating the substrate at a speed of 100-5000 rpmwhile at a temperature between 100-280° C.; (e) optionally ceasingrotation of the substrate; (f) laminating a second layer, comprising asolid-state cathode film or a lithium ion conducting separator at apressure of 10-2000 pounds per square inch (PSI) on to the heat-treatedpowder on at least one surface of the lithium ion conducting separatorelectrolyte; and g) cooling the heat-treated powder on at least onesurface of the lithium ion conducting separator electrolyte to roomtemperature.

In an seventeenth embodiment, disclosed herein is a method for coating aseparator, the method including a) providing a separator; b) providing amixture of a solvent and a composition comprisingA·(LiBH₄)·B·(LiX)·C·(LiNH₂), wherein X is fluorine, bromine, chlorine,iodine, or a combination thereof, and wherein 0.1≤A≤3, 0.1≤B≤4, and0≤C≤9; and c) depositing the mixture on the separator by spray coating,spin coating, dip coating, slot die coating, gravure coating, ormicrogravure coating.

In eighteenth embodiment, disclosed herein is a method for coating aseparator, the method including a) providing a separator; b) providingmolten A·(LiBH₄)·B·(LiX).C.(LiNH₂), wherein X is fluorine, bromine,chlorine, iodine, or a combination thereof, and wherein 0.1≤A≤3,0.1≤B≤4, and 0≤C≤9; and c) depositing the moltenA·(LiBH₄)·B·(LiX)·C·(LiNH₂) on the separator by spray coating, spincoating, dip coating, slot die coating, gravure coating, or microgravurecoating.

In a nineteenth embodiment, also disclosed herein are novelelectrochemical devices which incorporate the compositions set forthherein. For example, disclosed herein is an electrochemical cell havinga lithium metal negative electrode; a solid separator; and a positiveelectrode, wherein the solid separator includes a lithium-stuffed garnetand A·(LiBH₄)·B·(LiX)·C·(LiNH₂), wherein X is fluorine, bromine,chlorine, iodine, or a combination thereof, and wherein 0.1≤A≤3,0.1≤B≤4, and 0≤C≤9.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 shows one embodiment of an energy storage device 10 including acathode 20, a solid-state ion conductor 30, an anode 40, and currentcollectors 50 and 60.

FIG. 2A shows one embodiment of an energy storage device 210 including acathode 220, a solid-state ion conductor 230 which includes alithium-stuffed garnet 230A and a LBHI layer 230 B, an anode 240,current collectors 250 and 260, and a cathode-facing separator 270.

FIG. 2B shows another embodiment of an energy storage device 210including a cathode 220, a solid-state ion conductor 230 which includesa lithium-stuffed garnet 230A and a LBHI layer 230B, an anode 240,current collectors 250 and 260, and a catholyte 270 infiltrated withincathode 220.

FIG. 3 shows another embodiment of an energy storage device 310including a cathode 320, a solid-state ion conductor 330 which includesa lithium-stuffed garnet 330A and a LBHI layer 330B, an anode 340,current collectors 350 and 360, and a cathode-facing separator 370.

FIG. 4 shows a focused-ion beam scanning electron microscopy (FIB-SEM)image of a cross-section of a dip-coated LBHI-garnet, made in Example 4,having a coating of 3(LiBH₄):1(LiI) on a lithium-stuffed garnetfree-standing thin film, where the arrows A and B indicate regions ofLBHI infilling within the garnet. The scale bar is 25 μm.

FIG. 5 shows a dip-coated LBHI-garnet having a coating of3(LiBH₄):1(LiI) on a lithium-stuffed garnet free standing thin film,where LBHI penetration is measured by energy-dispersive x-ray (EDX)spectroscopy according to an iodine signal (gray, A). The scale bar is100 μm.

FIG. 6 shows comparative Kaplan-Meier electrochemical survival plots asa function of current density for uncoated garnet separators versusdip-coated LBHI-garnet separators, as described in Example 4.

FIG. 7 shows comparative calendar life plots of resistance versus timefor uncoated garnet separators (gray, A—top plot) versus dip-coated LBHIgarnet separators (black, B—bottom plot).

FIG. 8A shows an overlaid XRD plot for a dip-coated (top) and powder(bottom) LBHI, as described in Example 1.

FIG. 8B shows another XRD plot for a dip-coated LBHI with a wider rangefor 2θ, as described in Example 1.

FIG. 9 shows an Arrhenius plot of conductance (1/R) versus reciprocaltemperature (1000/T) (Kelvin) for a LBHI-coated lithium-stuffed garnet(top plot, labeled w/LBHI) and an uncoated lithium-stuffed garnet(bottom plot, labeled No LBHI), as described in Example 8.

FIG. 10 shows a plot for LBHI and LBHI with amide dopants versusconductivity at 60° C., where several measurements for compositionsLiBH₄:LiI (3:1), LiNH₂:LiBH₄:LiI (3:3:2), LiNH₂:LiBH₄:LiI (9:3:4), andLiNH₂:LiBH₄:LiI (9:3:2) are shown, as described in Example 7.

FIG. 11 shows a schematic for one embodiment of a testing apparatus inExample 4.

FIG. 12 shows LBHIN coated on a solid-state cathode film by drop castingmethod. In the figure, A is solid-state cathode film and B isLiNH₂:LiBH₄:LiI (3:3:2), as described in Example 11. The scale bar is 20μm.

FIG. 13 shows a lithium-stuffed garnet film (labeled C) and asolid-state cathode film (labeled A) which are bonded with a compositionof LiNH₂:LiBH₄:LiI (3:3:2) (labeled B) using molten LiNH₂:LiBH₄:LiI(3:3:2). The scale bar is 50 μm.

FIG. 14 shows test full cell structure of a lithium-stuffed garnet filmand a solid-state cathode film are bonded with composition ofLiNH₂:LiBH₄:LiCl (3:3:2) using molten LiNH₂:LiBH₄:LiI (3:3:2). In thefigure, A is current collector; B is a sulfide containing solid-statecathode; C is 3·(LiBH₄)·2·(LiCl)·3·(LiNH₂); D is Li-stuffed garnet film;E is evaporated lithium; and F is current collector.

FIG. 15 shows cycling data of the cell illustrated in FIG. 14 whichconsisted of lithium-stuffed garnet film and a solid-state cathode filmbonded with molten composition of LiNH₂:LiBH₄:LiCl (3:3:2).

FIG. 16 shows an area-specific resistance (ASR) plot of the cellillustrated in FIG. 14 on the first electrochemical cycle.

FIG. 17 shows conductivity data for LiNH₂:LiBH₄:LiCl (3:3:2) (labeledLBHClN) and LiNH₂:LiBH₄:LiI (3:3:2) (labeled LBHlN).

DETAILED DESCRIPTION OF THE INVENTION

The following description is presented to enable one of ordinary skillin the art to make and use the inventions set forth herein and toincorporate these inventions in the context of particular applications.Various modifications, as well as a variety of uses in differentapplications will be readily apparent to those skilled in the art, andthe general principles defined herein may be applied to a wide range ofembodiments. Thus, the inventions herein are not intended to be limitedto the embodiments presented, but is to be accorded the widest scopeconsistent with the principles and novel features disclosed herein.

Furthermore, any element in a claim that does not explicitly state“means for” performing a specified function, or “step for” performing aspecific function, is not to be interpreted as a “means” or “step”clause as specified in pre-America Invents Act (AIA) 35 U.S.C. Section112, Paragraph 6 or post-AIA 35 U.S.C. Section 112(f). In particular,the use of “step of” or “act of” in the Claims herein is not intended toinvoke the provisions of pre-AIA 35 U.S.C. Section 112, Paragraph 6 orpost-AIA 35 U.S.C. Section 112(f).

All the features disclosed in this specification, (including anyaccompanying claims, abstract, and drawings) may be replaced byalternative features serving the same, equivalent or similar purpose,unless expressly stated otherwise. Thus, unless expressly statedotherwise, each feature disclosed is one example only of a genericseries of equivalent or similar features.

Please note, if used, the labels left, right, front, back, top, bottom,forward, reverse, clockwise and counter clockwise have been used forconvenience purposes only and are not intended to imply any particularfixed direction. Instead, they are used to reflect relative locationsand/or directions between various portions of an object.

General

Disclosed herein are compositions that include LiBH₄ optionally with aLithium Halide (e.g., LiCl, LiBr, or LiI) and optionally with a Li Amide(e.g., LiNH₂). Also set forth herein are methods for making and usingsuch compositions to prepare thin film solid electrolytes forsolid-state lithium-secondary batteries. Also set forth herein arecertain improved solid electrolytes which are prepared by passivatingthe defects in solid separators (e.g., lithium-stuffed garnet) bycoating or co-formulating chemical agents [e.g.,LiI(LiBH₄).(LiX).(LiNH₂)] with the solid separators.

Definitions

If a definition provided in any material incorporated by referenceherein conflicts with a definition provided herein, the definitionprovided herein controls.

As used herein, the phrase “solid-state cathode” or “solid-statepositive electrode” refers to a type of “positive electrode” definedherein. All components in this solid-state cathode film are in solidform. The solid-state cathode includes active cathode materials asdefined herein, solid-state catholyte as defined herein, optionally aconductive additive, and optionally binders. The solid-state cathode arein some examples densified films.

As used herein, the phrase “current collector” refers to a component orlayer in a secondary battery through which electrons conduct, to or froman electrode in order to complete an external circuit, and which are indirect contact with the electrode to or from which the electronsconduct. In some examples, the current collector is a metal (e.g., Al,Cu, or Ni, steel, alloys thereof, or combinations thereof) layer whichis laminated to a positive or negative electrode. In some examples, thecurrent collector is Al. In some examples, the current collector is Cu.In some examples, the current collector is Ni. In some examples, thecurrent collector is steel. In some examples, the current collector isan alloy of Al. In some examples, the current collector is an alloy ofCu. In some examples, the current collector is an alloy of steel. Insome examples, the current collector is Al. In some examples, thecurrent collector comprises a combination of the above metals. Duringcharging and discharging, electrons move in the opposite direction tothe flow of Li ions and pass through the current collector when enteringor exiting an electrode.

As used herein, the phrase “at least one member selected from thegroup,” includes a single member from the group, more than one memberfrom the group, or a combination of members from the group. At least onemember selected from the group consisting of A, B, and C includes, forexample, A, only, B, only, or C, only, as well as A and B as well as Aand C as well as B and C as well as A, B, and C or any other allcombinations of A, B, and C.

As used herein, the phrase “slot casting,” or “slot die coating” refersto a deposition process whereby a substrate is coated, or deposited,with a solution, liquid, slurry, or the like by flowing the solution,liquid, slurry, or the like, through a slot or mold of fixed dimensionsthat is placed adjacent to, in contact with, or onto the substrate ontowhich the deposition or coating occurs. In some examples, slot castingincludes a slot opening of about 1 to 100 μm.

As used herein, the phrase “dip casting” or “dip coating” refers to adeposition process whereby a substrate is coated, or deposited, with asolution, liquid, slurry, or the like, by moving the substrate into andout of the solution, liquid, slurry, or the like, often in a verticalfashion, sometimes at an angle, such as 45° from the surface of thesolution, liquid slurry, or the like.

As used herein, the phrase “solid-state catholyte,” or the term“catholyte” refers to an ion conductor that is intimately mixed with, orsurrounded by, a cathode (i.e., positive electrode) active material(e.g., a metal fluoride optionally including lithium).

As used herein, the term “electrolyte,” refers to a material that allowsions, e.g., Li⁺, to migrate therethrough, but which does not allowelectrons to conduct therethrough. Electrolytes are useful forelectrically insulating the cathode and anode of a secondary batterywhile allowing ions, e.g., Li⁺, to transmit through the electrolyte.Solid electrolytes, in particular, rely on ion hopping and/or diffusionthrough rigid structures. Solid electrolytes may be also referred to asfast ion conductors or super-ionic conductors. In this case, a solidelectrolyte layer may be also referred to as a solid electrolyteseparator.

As used herein, the term “anolyte,” refers to an ionically conductivematerial that is mixed with, or layered upon, or laminated to, an anodematerial or anode current collector.

As used herein the term “making,” refers to the process or method offorming or causing to form the object that is made. For example, makingan energy storage electrode includes the process, process steps, ormethod of causing the electrode of an energy storage device to beformed. The end result of the steps constituting the making of theenergy storage electrode is the production of a material that isfunctional as an electrode.

As used herein the phrase “energy storage electrode,” refers to, forexample, an electrode that is suitable for use in an energy storagedevice, e.g., a lithium rechargeable battery or Li-secondary battery. Asused herein, such an electrode is capable of conducting electrons and Liions as necessary for the charging and discharging of a rechargeablebattery.

As used herein, the phrase “providing” refers to the provision of,generation or, presentation of, or delivery of that which is provided.

As used herein, the phrase “lithium-stuffed garnet” refers to oxidesthat are characterized by a crystal structure related to a garnetcrystal structure. Examples of lithium-stuffed garnets are set forth inU.S. Patent Application Publication No. 2015/0099190, which publishedApr. 9, 2015, and was filed Oct. 7, 2014 as Ser. No. 14/509,029, and isincorporated by reference herein in its entirety for all purposes. Thisapplication describes Li-stuffed garnet solid-state electrolytes used insolid-state lithium rechargeable batteries. These Li-stuffed garnetsgenerally having a composition according toLi_(A)La_(B)M′_(C)M″_(D)Zr_(E)O_(F),Li_(A)La_(B)M′_(C)M″_(D)Ta_(E)O_(F), orLi_(A)La_(B)M′_(C)M″_(D)Nb_(E)O_(F), wherein 4≤A≤8.5, 1.5≤B≤4, 0≤C≤2,0≤D≤2; 0≤E≤3, 10≤F≤13, and M′ and M″ are each, independently in eachinstance selected from Ga, Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb,and Ta, or Li_(a)La_(b)Zr_(c)Al_(d)Me″_(e)O_(f), wherein 5<a<8.5; 2<b<4;0<c≤2.5; 0≤d≤2; 0<e<2, and 10<f<13 and Me″ is a metal selected from Ga,Nb, Ta, V, W, Mo, and Sb and as otherwise described in U.S. PatentApplication Publication No. 2015/0099190. As used herein,lithium-stuffed garnets, and garnets, generally, include, but are notlimited to, Li_(7±δLa) ₃(Zr_(t1)+Nb_(t2)+Ta_(t3))O₁₂+0.35Al₂O₃; wherein6 is from 0 to 3 and (t1+t2+t3=2) so that the La:(Zr/Nb/Ta) ratio is3:2. For example, δ is 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9,1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3,2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0. In some examples, the Li-stuffedgarnet herein has a composition of Li_(7±δ)Li₃Zr₂O₁₂.xAl₂O₃. In yetanother embodiment, the Li-stuffed garnet herein has a composition ofLi_(7±δ)Li₃Zr₂O₁₂·0.22Al₂O₃. In yet other examples, the Li-stuffedgarnet herein has a composition of Li_(7±δ)Li₃Zr₂O₁₂·0.35Al₂O₃. Incertain other examples, the Li-stuffed garnet herein has a compositionof Li_(7±δ)Li₃Zr₂O₁₂·0.5Al₂O₃. In another example, the Li-stuffed garnetherein has a composition of Li_(7±δ)Li₃Zr₂O₁₂·0.75Al₂O₃. Also, L-stuffedgarnets used herein include, but are not limited to,Li_(x)La₃Zr₂O_(F)+yAl₂O₃, wherein x ranges from 5.5 to 9; and y rangesfrom 0.05 to 1. In these examples, subscripts x, y, and F are selectedso that the Li-stuffed garnet is charge neutral. In some examples x is 7and y is 1.0. In some examples, x is 5 and y is 1.0. In some examples, xis 6 and y is 1.0. In some examples, x is 8 and y is 1.0. In someexamples, x is 9 and y is 1.0. In some examples x is 7 and y is 0.35. Insome examples, x is 5 and y is 0.35. In some examples, x is 6 and y is0.35. In some examples, x is 8 and y is 0.35. In some examples, x is 9and y is 0.35. In some examples x is 7 and y is 0.7. In some examples, xis 5 and y is 0.7. In some examples, x is 6 and y is 0.7. In someexamples, x is 8 and y is 0.7. In some examples, x is 9 and y is 0.7. Insome examples x is 7 and y is 0.75. In some examples, x is 5 and y is0.75. In some examples, x is 6 and y is 0.75. In some examples, x is 8and y is 0.75. In some examples, x is 9 and y is 0.75. In some examplesx is 7 and y is 0.8. In some examples, x is 5 and y is 0.8. In someexamples, x is 6 and y is 0.8. In some examples, x is 8 and y is 0.8. Insome examples, x is 9 and y is 0.8. In some examples x is 7 and y is0.5. In some examples, x is 5 and y is 0.5. In some examples, x is 6 andy is 0.5. In some examples, x is 8 and y is 0.5. In some examples, x is9 and y is 0.5. In some examples x is 7 and y is 0.4. In some examples,x is 5 and y is 0.4. In some examples, x is 6 and y is 0.4. In someexamples, x is 8 and y is 0.4. In some examples, x is 9 and y is 0.4. Insome examples x is 7 and y is 0.3. In some examples, x is 5 and y is0.3. In some examples, x is 6 and y is 0.3. In some examples, x is 8 andy is 0.3. In some examples, x is 9 and y is 0.3. In some examples x is 7and y is 0.22. In some examples, x is 5 and y is 0.22. In some examples,x is 6 and y is 0.22. In some examples, x is 8 and y is 0.22. In someexamples, x is 9 and y is 0.22. Also, Li-stuffed garnets as used hereininclude, but are not limited to, Li_(x)La₃Zr₂O₁₂+yAl₂O₃, wherein y isfrom 0 to 1 and includes 0 and 1. In one embodiment, the Li-stuffedgarnet herein has a composition of Li₇Li₃Zr₂O₁₂.

As used herein, garnet or Li-stuffed garnet does not include YAG-garnets(i.e., yttrium aluminum garnets, or, e.g., Y₃Al₅O₁₂). As used herein,garnet does not include silicate-based garnets such as pyrope,almandine, spessartine, grossular, hessonite, or cinnamon-stone,tsavorite, uvarovite and andradite and the solid solutionspyrope-almandine-spessarite and uvarovite-grossular-andradite. Garnetsherein do not include nesosilicates having the general formulaX₃Y₂(SiO₄)₃ wherein X is Ca, Mg, Fe, and, or, Mn; and Y is Al, Fe, and,or, Cr.

As used herein, the phrases “garnet precursor chemicals,” “chemicalprecursor to a garnet-type electrolyte,” “precursors to garnet” and“garnet precursor materials” refer to chemicals which react to form alithium-stuffed garnet material described herein. These chemicalprecursors include, but are not limited to lithium hydroxide (e.g.,LiOH), lithium oxide (e.g., Li₂O), lithium carbonate (e.g., LiCO₃),zirconium oxide (e.g., ZrO₂), lanthanum oxide (e.g., La₂O₃), lanthanumhydroxide (e.g., La(OH)₃), aluminum oxide (e.g., Al₂O₃), aluminumhydroxide (e.g., Al(OH)₃), AlOOH, aluminum (e.g., Al), Boehmite,gibbsite, corundum, aluminum nitrate (e.g., Al(NO₃)₃), aluminum nitratenonahydrate, niobium oxide (e.g., Nb₂O₅), gallium oxide (Ga₂O₃), andtantalum oxide (e.g., Ta₂O₅). Other precursors to garnet materials,known in the relevant field to which the instant disclosure relates, maybe suitable for use with the methods set forth herein.

As used herein the phrase “garnet-type electrolyte,” refers to anelectrolyte that includes a lithium-stuffed garnet material describedherein as a Li⁺ ion conductor. The advantages of Li-stuffed garnetsolid-state electrolytes are many, including as a substitution forliquid, flammable electrolytes commonly used in lithium rechargeablebatteries.

As used herein, the phrase “doped with alumina” means that Al₂O₃ is usedto replace certain components of another material, e.g., a garnet. Alithium-stuffed garnet that is doped with Al₂O₃ refers to garnet whereinaluminum (Al) substitutes for an element in the lithium-stuffed garnetchemical formula, which may be, for example, Li or Zr.

As used herein, the phrase “subscripts and molar coefficients in theempirical formulas are based on the quantities of raw materialsinitially batched to make the described examples” means the subscripts,(e.g., 7, 3, 2, 12 in Li₇La₃Zr₂O₁₂ and the coefficient 0.35 in0.35Al₂O₃) refer to the respective elemental ratios in the chemicalprecursors (e.g., LiOH, La₂O₃, ZrO₂, Al₂O₃) used to prepare a givenmaterial, (e.g., Li₇La₃Zr₂O₁₂.0.35Al₂O₃), unless specified otherwise.

As used herein, the phrase “electrochemical device” refers to an energystorage device, such as, but not limited to a Li-secondary battery thatoperates or produces electricity or an electrical current by anelectrochemical reaction, e.g., a conversion chemistry reaction such as3Li+FeF₃←3LiF+Fe.

As used herein, the phrase “film thickness” refers to the distance, ormedian measured distance, between the top and bottom faces of a film. Asused herein, the top and bottom faces refer to the sides of the filmhaving the largest surface area.

As used herein, the term “grains” refers to domains of material withinthe bulk of a material that have a physical boundary which distinguishesthe grain from the rest of the material. For example, in some materialsboth crystalline and amorphous components of a material, often havingthe same chemical composition, are distinguished from each other by theboundary between the crystalline component and the amorphous component,or a boundary between regions of different crystalline orientation. Theapproximate diameter of the region between boundaries of a crystallinecomponent, or of an amorphous component, is referred herein as the grainsize. Grains may be observed in SEM if appropriate techniques areapplied to bring the grains into higher relief; these techniques mayinclude chemical etching or exposure to high energy electron beams.

As used herein, the term “diameter (d₉₀)” refers to the size, in adistribution of sizes, measured by microscopy techniques or otherparticle size analysis techniques, including, but not limited to,scanning electron microscopy or dynamic light scattering. D₉₀ includesthe characteristic dimension at which 90% of the particles are smallerthan the recited size. Similarly, the term “diameter (d₅₀)” includes thecharacteristic dimension at which 50% of the particles are smaller thanthe recited size. Similarly, the term “diameter (d₁₀)” includes thecharacteristic dimension at which 10% of the particles are smaller thanthe recited size. These figures may be calculated on a per-volume orper-number basis.

As used herein the phrase “active anode material” refers to an anodematerial that is suitable for use in a Li rechargeable battery thatincludes an active cathode material as defined above. In some examples,the active material is Lithium metal.

As used herein the phrase “casting a film,” refers to the process ofdelivering or transferring a liquid or a slurry into a mold, or onto asubstrate, such that the liquid or the slurry forms, or is formed into,a film. Casting may be done via doctor blade, meyer rod, comma coater,gravure coater, microgravure, reverse comma coater, slot dye, slipand/or tape casting, and other methods known to those skilled in theart.

As used herein the phrase “applying a pressure,” refers to a processwhereby an external device, e.g., a calender, induces a pressure inanother material.

As used herein the phrase “average pore diameter dimensions of about 5nm to about 1 μm” refers to a material that has pores wherein the innerdiameter of the pores therein are physically spaced by about 5 nm, fornanopores for example, to about 1 μm, for micropores for example.

As used herein the term “infiltrated,” refers to the state wherein onematerial passes into another material, or when one material is caused tojoin another material. For example, if a porous Garnet is infiltratedwith LBHI, this refers to the process whereby LBHI is caused to passinto and intimately mix with the porous Garnet.

As used herein, the terms “separator,” and “Li⁺ ion-conductingseparator,” are used interchangeably with separator being a short-handreference for Li⁺ ion-conducting separator, unless specified otherwiseexplicitly. A separator refers to a solid electrolyte which conducts Li⁺ions, is substantially insulating to electrons, and which is suitablefor use as a physical barrier or spacer between the positive andnegative electrodes in an electrochemical cell or a rechargeablebattery. A separator, as used herein, is substantially insulating whenthe separator's lithium ion conductivity is at least 10³, and typically10⁶ times, greater than the separator's electron conductivity. Aseparator can be a film, monolith, or pellet. Unless explicitlyspecified to the contrary, a separator as used herein is stable when incontact with lithium metal.

As used here, the phrase “inorganic solid-state electrolyte,” is usedinterchangeably with the phrase “solid separator” refers to a materialwhich does not include carbon and which conducts atomic ions (e.g., Li⁺)but does not conduct electrons. An inorganic solid-state electrolyte isa solid material suitable for electrically isolating the positive andnegative electrodes of a lithium secondary battery while also providinga conduction pathway for lithium ions. Example inorganic solid-stateelectrolytes include oxide electrolytes and sulfide electrolytes, whichare further defined below. Non-limiting example sulfide electrolytes arefound, for example, in U.S. Pat. No. 9,172,114, which issued Oct. 27,2015, and also in US Patent Application Publication No. 2017-0162901 A1,which published Jun. 8, 2017, and was filed as U.S. patent applicationSer. No. 15/367,103 on Dec. 1, 2016, the entire contents of which areherein incorporated by reference in its entirety for all purposes.Non-limiting example oxide electrolytes are found, for example, in USPatent Application Publication No. 2015-0200420 A1, which published Jul.16, 2015, the entire contents of which are herein incorporated byreference in its entirety for all purposes. In some examples, theinorganic solid-state electrolyte also includes a polymer.

As used herein, the phrase “lithium interfacial resistance,” refers tothe interfacial resistance of a material towards the incorporation ofLi⁺ ions. A lithium interfacial ASR (ASR_(interface)) is calculated fromthe interfacial resistance (R_(interface)), by the equationASR_(interface)=R_(interface)*A/2, where A is the area of the electrodesin contact with the separator and the factor of 2 accounts for 2interfaces when measured in a symmetric cell andR_(interface)=R_(total)−R_(bulk).

As used herein “ASR” refers to area-specific resistance. ASR is measuredusing electrochemical impedance spectroscopy (EIS). EIS can be performedon a Biologic VMP3 instrument or an equivalent thereof. In an ASRmeasurement to lithium contacts are deposited on two sides of a sample.An AC voltage of 25 mV rms is applied across a frequency of 300 kHz-0.1mHz while the current is measured. EIS partitions the ASR into the bulkcontribution and the interfacial ASR contribution, by resolving twosemicircles in a Nyquist plot.

As used herein, the term “LIRAP” refers to a lithium rich antiperovskiteand is used synonymously with “LOC” or “Li₃OCl”. The composition ofLIRAP is aLi₂O+bLiX+cLiOH+dAl₂O₃ where X═Cl, Br, and/or I, a/b=0.7-9,c/a=0.01-1, d/a=0.001-0.1.

As used herein, the term “LPS+X” refers to a lithium conductingelectrolyte comprising Li, P, S, and X, where X═Cl, Br, and/or I. Forexample, “LSPI” refers to a lithium conducting electrolyte comprisingLi, P, S, and I. More generally, it is understood to includeaLi₂S+bP₂S_(y)+cLiX where X═Cl, Br, and/or I and where y=3-5 and wherea/b=2.5-4.5 and where (a+b)/c=0.5-15.

As used herein, “LSS” refers to lithium silicon sulfide which can bedescribed as Li₂S—SiS₂, Li—SiS₂, Li—S—Si, and/or a catholyte consistingessentially of Li, S, and Si. LSS refers to an electrolyte materialcharacterized by the formula Li_(x)Si_(y)S_(z) where 0.33≤x≤0.5,0.1≤y≤0.2, 0.4≤z≤0.55, and it may include up to 10 atomic % oxygen. LSSalso refers to an electrolyte material comprising Li, Si, and S. In someexamples, LSS is a mixture of Li₂S and SiS₂. In some examples, the ratioof Li₂S:SiS₂ is 90:10, 85:15, 80:20, 75:25, 70:30, 2:1, 65:35, 60:40,55:45, or 50:50 molar ratio. LSS may be doped with compounds such asLi_(x)PO_(y), Li_(x)BO_(y), Li₄SiO₄, Li₃MO₄, Li₃MO₃, PS_(x), and/orlithium halides such as, but not limited to, LiI, LiCl, LiF, or LiBr,wherein 0<x≤5 and 0<y≤5.

As used herein, the term “SLOPS” refers to unless otherwise specified, a60:40 molar ratio of Li₂S:SiS₂ with 0.1-10 mol. % Li₃PO₄. In someexamples, “SLOPS” includes Li₁₀Si₄S₁₃ (50:50 Li₂S:SiS₂) with 0.1-10 mol.% Li₃PO₄. In some examples, “SLOPS” includes Li₂₆Si₇S₂₇ (65:35Li₂S:SiS₂) with 0.1-10 mol. % Li₃PO₄. In some examples, “SLOPS” includesLi₄SiS₄ (67:33 Li₂S:SiS₂) with 0.1-5 mol. % Li₃PO₄. In some examples,“SLOPS” includes Li₁₄Si₃S₁₃ (70:30 Li₂S:SiS₂) with 0.1-5 mol. % Li₃PO₄.In some examples, “SLOPS” is characterized by the formula (1−x)(60:40Li₂S:SiS₂)*(x)(Li₃PO₄), wherein x is from 0.01 to 0.99. As used herein,“LBS-POX” refers to an electrolyte composition of Li₂S:B₂S₃:Li₃PO₄: LiXwhere X is a halogen (X═F, Cl, Br, I). The composition can includeLi₃BS₃ or Li₅B₇S₁₃ doped with 0-30% lithium halide such as LiI and/or0-10% Li₃PO₄.

As used herein, the term “LSTPS” refers to an electrolyte materialhaving Li, Si, P, Sn, and S chemical constituents. As used herein,“LSPSO,” refers to LSPS that is doped with, or has, O present. In someexamples, “LSPSO,” is a LSPS material with an oxygen content between0.01 and 10 atomic %. As used herein, “LATP,” refers to an electrolytematerial having Li, As, Sn, and P chemical constituents. As used herein“LAGP,” refers to an electrolyte material having Li, As, Ge, and Pchemical constituents. As used herein, “LXPSO” refers to a catholytematerial characterized by the formula Li_(a) MP_(b)S_(c)O_(d), where Mis Si, Ge, Sn, and/or Al, and where 2≤a≤8, 0.5≤b≤2.5, 4≤c≤12, and d<3.LXPSO refers to LXPS, as defined above, and having oxygen doping at from0.1 to about 10 atomic %. LPSO refers to LPS, as defined above, andhaving oxygen doping at from 0.1 to about 10 atomic %.

As used herein, “LTS” refers to a lithium tin sulfide compound which canbe described as Li₂S:SnS₂:As₂S₅, Li₂S—SnS₂, Li₂S—SnS, Li—S—Sn, and/or acatholyte consisting essentially of Li, S, and Sn. The composition maybe Li_(x)Sn_(y)S_(z) where 0.25≤x≤0.65, 0.05≤y≤0.2, and 0.25≤z≤0.65. Insome examples, LTS is a mixture of Li₂S and SnS₂ in the ratio of 80:20,75:25, 70:30, 2:1, or 1:1 molar ratio. LTS may include up to 10 atomic %oxygen. LTS may be doped with Bi, Sb, As, P, B, Al, Ge, Ga, and/or Inand/or lithium halides such as, but not limited to, LiI, LiCl, LiF, orLiBr.

As used herein, the term “LATS” refers to an LTS further includingArsenic (As).

As used here, the term “transparent” refers to a material that has atransmission coefficient of greater than 0.9 when measured with incidentlight at a wavelength between 400-700 nm. As used here, the term“translucent” refers to a material that has a transmission coefficientof between 0.1-0.9 when measured with incident light at a wavelengthbetween 400-700 nm.

As used herein, the phrase “transmission coefficient,” refers to theratio of the amount of incident light which transmits through a materialwith respect to the total amount of incident light. A transmissioncoefficient of 0.5 means that half of the incident light which impingesupon a material transmits through that material.

As used herein, the term “thin film” refers to a film having thecomponents, compositions, or materials described herein where the filmhas an average thickness dimension of about 10 nm to about 100 μm. Insome examples, thin refers to a film that is less than about 1 μm, 10μm, or 50 μm in thickness.

As used herein, the term “monolith,” refers to a separator having adensity which is at least as dense as a film, but wherein the monolithis thicker than a thin film by at least a factor of two (2) or more. Amonolith is to be distinguished from a composite in that a compositeincludes more than one type of material whereas a monolith ishomogeneous and made of a single type of material. That is, a “monolith”refers to an object having a single or uniform body. A monolith is a“shaped, fabricated, intractable article with a homogeneousmicrostructure which does not exhibit any structural componentsdistinguishable by optical microscopy.” Typical fabrication techniquesfor forming the article include, but are not limited to, cold pressingor hot pressing of a polymeric material, and using a reactive processingtechnique such as reaction injection molding, crosslinking, sol-gelprocessing, sintering, and the like As used herein, a monolith and asintered film have substantially the same density when both are preparedsubstantially defect free. Herein, substantially defect free is amaterial having approximately 0.0001% defects per volume.

As used herein, the term “pellet” refers to a small unit of bulkymaterial compressed into any of several shapes and sizes, e.g.,cylindrical, rectangular, or spherical. The compressed material isdisc-shaped and may be 5-20 cm in diameter and 0.5 to 2 cm in height.Typically, the compressed material is disc-shaped and 10 cm in diameterand 1 cm in height. Pellets may also include additional agents to helpbind the material compressed into the pellet. In some examples, theseadditional agents are referred to as binding agents and may include, butare not limited to, polymers such as poly(ethylene)oxide. In someexamples, polyvinyl butyral is used as a binding agent. Pellets aretypically made by pressing a collection of powder materials in a press.This pressing makes the powder materials adhere to each other andincreases the density of the collection of powder material when comparedto the density of the collection of powder material before pressing. Insome instances, the powder material is heated and/or an electricalcurrent is passed through the powder material during the pressing.

As used herein, the term “pressed pellet” refers to a pellet having beensubmitted to a pressure (e.g., 5000 PSI) to further compress the pellet.

As used herein, the term “oxide” refers to a chemical compound thatincludes at least one oxygen atom and one other element in the chemicalformula for the chemical compound. For example, an “oxide” isinterchangeable with “oxide electrolytes.” Non-limiting examples ofoxide electrolytes are found, for example, in U.S. Patent ApplicationPublication No. 2015/0200420, published Jul. 16, 2015, the contents ofwhich are incorporated herein by reference in their entirety.

As used herein, the term “sulfide” refers to refers to a chemicalcompound that includes at least one sulfur atom and one other element inthe chemical formula for the chemical compound. For example, a “sulfide”is interchangeable with “sulfide electrolytes.” Non-limiting examples ofsulfide electrolytes are found, for example, in U.S. Pat. No. 9,172,114,issued Oct. 27, 2015, and also in U.S. Patent Application PublicationNo. 2017-0162901 A1, which published Jun. 8, 2017, and was filed as U.S.patent application Ser. No. 15/367,103 on Dec. 1, 2016, the entirecontents of which are herein incorporated by reference in its entiretyfor all purposes.

As used herein, the term “sulfide-halide” refers to a chemical compoundthat includes at least one sulfur atom, at least one halogen atom, andone other element in the chemical formula for the chemical compound.

As used herein, the term “total effective lithium ion conductivity” of amaterial refers to L/R_(bulk)A, where L is the total thickness of thematerial, A is the measurement area, for example, the interfacialcontact area of electrodes in contact with the material, and R_(bulk) isthe bulk resistance of the material measured, for example, byelectrochemical impedance spectroscopy.

As used herein, the term “LBHI” or “LiBHI” refers to a lithiumconducting electrolyte having Li, B, H, and I. More generally, it isunderstood to include aLiBH₄+bLiX where X═Cl, Br, and/or I and wherea:b=7:1, 6:1, 5:1, 4:1, 3:1, 2:1, or within the range a/b=2-4. LBHI mayfurther include nitrogen in the form of aLiBH₄+bLiX+cLiNH₂ where(a+c)/b=2-4 and c/a=0-10.

As used herein, the term “LBHXN” refers to a composition characterizedas A·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X is fluorine (F), bromine (Br),chloride (Cl), iodine (I), or a combination thereof, and wherein0.1≤A≤4, 0.1≤B≤4, and 0≤C≤9.

As used herein, the term “conformally bonded” refers to the bonding of acomposition to a substrate where the idiosyncratic defects of thesubstrate are unchanged yet masked or smoothened by the bonding of thecomposition to the substrate.

As used herein, the term “gravure coating” or “microgravure coating”refers to a process in which a substrate is contacted with a liquid viaa roll-to-roll process. A roll surface is engraved with a pattern ofcells that provide a desired coating volume. The roll is mounted inbearings and is rotated while partially submerged in a receptacleholding the liquid to be coated onto the substrate. Rotation of the rollpermits the substrate to acquire the coating, which is pre-metered witha flexible blade (e.g., a doctor blade) as the roll rotates toward acontact point with the substrate. Typically, gravure coating includes abacking roll having approximately the same diameter as the engravedroll.

As used herein, the term “through-pores” in a material refers to a gapor void that extends through the entirety of the material.

As used herein, the term “surface pores” in a material refers to a gap,cavity, or void that resides at the surface of a substrate.

As used herein, the term “amorphous,” refers to a material that is notcrystalline or that does not contain a majority crystalline phase.Amorphous refers to a material that does not evidence a crystallineproperty, for example, well-defined x-ray diffraction peaks as measuredby x-ray diffraction. An amorphous material is at least primarilyamorphous and characterized as having more amorphous components thancrystalline components. Substantially amorphous refers to a materialthat does not include well defined x-ray diffraction peaks or that ischaracterized by an x-ray diffraction pattern that includes broadreflections that are recognized by a person having ordinary skill in theart as having the majority constituent component phase as an amorphousphase. A material that is substantially amorphous may have nano-sizeddomains of crystallinity, but which are still characterized by an x-raydiffraction pattern to be primarily in an amorphous phase. In asubstantially amorphous material, transmission electron microscopy (TEM)selected area diffraction pattern (SADP) may evidence regions ofcrystallinity, but would also evidence a majority of the volume of thematerial as amorphous.

As used herein, the term “semiamorphous” or “semi-crystalline” refers toa composition having both crystalline and amorphous domains. Asemi-crystalline material includes both nanocrystalline and/ormicrocrystalline components in addition to amorphous components. Asemi-crystalline material is a material that is partially crystallizedor is a material that includes some crystalline bulk and some amorphousbulk. For example, a material heated to its crystallization temperature,but subsequently cooled before the entirety of the material is able tocrystallize, completely, is referred to herein as semi-crystallinematerial. As used herein, a semi-crystalline material can becharacterized by an XRD powder pattern in which the primary peak ofhighest intensity has a full width at half maximum of at least 1° (2Θ),or at least 2° (2Θ), or at least 3° (2Θ).

As used herein, “SLOBS” includes, unless otherwise specified, a 60:40molar ratio of Li₂S:SiS₂ with 0.1-10 mol. % LiBH₄. In some examples,“SLOBS” includes Li₁₀Si₄S₁₃ (50:50 Li₂S:SiS₂) with 0.1-10 mol. % LiBH₄.In some examples, “SLOBS” includes Li₂₆Si₇S₂₇ (65:35 Li₂S:SiS₂) with0.1-10 mol. % LiBH₄. In some examples, “SLOBS” includes Li₄SiS₄ (67:33Li₂S:SiS₂) with 0.1-5 mol. % LiBH₄. In some examples, “SLOBS” includesLi₁₄Si₃S₁₃ (70:30 Li₂S:SiS₂) with 0.1-5 mol. % LiBH₄. In some examples,“SLOBS” is characterized by the formula (1−x)(60:40Li₂S:SiS₂)*(x)(Li₃BO₄), wherein x is from 0.01 to 0.99. As used herein,“LBS-BOX” refers to an electrolyte composition of Li₂S:B₂S₃:LiBH₄:LiXwhere X is a halogen (X═F, Cl, Br, I). The composition can includeLi₃BS₃ or Li₅B₇S₁₃ doped with 0-30% lithium halide such as LiI and/or0-10% Li₃PO₄.

As used herein, the phrase “characterized by the formula” refers to adescription of a chemical compound by its chemical formula.

As used herein, the phrase “doped with Nb, Ga, and/or Ta” means that Nb,Ga, and/or Ta is used to replace certain components of another material,for example, a garnet. A lithium-stuffed garnet that is doped with Nb,Ga, and/or Ta refers to a lithium-stuffed garnet wherein Nb, Ga, and/orTa substitutes for an element in the lithium-stuffed garnet chemicalformula, which may be, for example, Li and/or Zr.

As used herein, the term “defect” refers to an imperfection or adeviation from a pristine structure that interacts with (i.e., absorbs,scatters, reflects, refracts, and the like) light. Defects may include,but are not limited to, a pore, a grain boundary, a dislocation, acrack, a separation, a chemical inhomogeneity, or a phase segregation oftwo or more materials in a solid material. A perfect crystal is anexample of a material that lacks defects. A nearly 100% dense oxideelectrolyte that has a planar surface, with substantially no pitting,inclusions, cracks, pores, or divots on the surface, is an example of anelectrolyte that is substantially lacking defects. Defects can include asecond phase inclusion (e.g., a Li₂S phase inside a LPSI electrolyte).Defects can include a pore inclusion. Defects can include a grainboundary wherein two adjacent grains have a region where theirseparation is greater than 10 nm. Defects can include pores in a porousseparator.

As used herein, the term “about” when qualifying a number, e.g., about15% w/w, refers to the number qualified and optionally the numbersincluded in a range about that qualified number that includes ±10% ofthe number. For example, about 15 w/w includes 15% w/w as well as 13.5%w/w, 14% w/w, 14.5% w/w, 15.5% w/w, 16% w/w, or 16.5% w/w. For example,“about 75° C,” includes 75° C. as well 68° C., 69° C., 70° C., 71° C.,72° C., 73° C., 74° C., 75° C., 76° C., 77° C., 78° C., 79° C., 80° C.,81° C., 82° C., or 83° C.

As used herein, the phrase “charge neutral” refers to two or moreelements of a chemical compound having an ionic charge where the sum ofthe ionic charges is zero. For example, the phrase “wherein u, v, x, y,and z are selected so that the lithium-stuffed garnet oxide is chargeneutral” refers to the summation of ionic charges equaling zero for eachelement the u, v, x, y, or z refers to.

As used herein, the phrase “transmission properties of the compositionvary by less than 50% over a surface area of at least 100 μm²”refers toa property (e.g., transmission coefficient) which is constant, uniform,or includes the given variance over the given surface area or volume.

As used herein, the phrase “bonded to defects” refers to a compositionthat is fixed to a substrate having imperfections. For example, acomposition bonded to defects as defined herein includes infilling,joining, or passivation of a substrate having imperfections.

As used herein the term “porous” or “porosity” refers to a material thatincludes pores, e.g., nanopores, mesopores, or micropores.

As used herein, the phrase “porosity as determined by SEM” refers tomeasurement of density by using image analysis software to analyze ascanning electron micrograph. For example, first, a user or softwareassigns pixels and/or regions of an image as porosity. Second, the areafraction of those regions is summed. Finally, the porosity fractiondetermined by SEM is equal to the area fraction of the porous region ofthe image.

As used herein, the phrases “electrochemical cell” or “battery cell”shall mean a single cell including a positive electrode and a negativeelectrode, which have ionic communication between the two using anelectrolyte. In some embodiments, the same battery cell includesmultiple positive electrodes and/or multiple negative electrodesenclosed in one container.

As used herein the phrase “electrochemical stack,” refers to one or moreunits which each include at least a negative electrode (e.g., Li, LiC₆),a positive electrode (e.g., Li-nickel-manganese-oxide or FeF₃,optionally combined with a solid-state electrolyte or a gelelectrolyte), and a solid electrolyte (e.g., an oxide electrolyte setforth herein) between and in contact with the positive and negativeelectrodes. In some examples, between the solid electrolyte and thepositive electrode, there is an additional layer comprising a compliant(e.g., gel electrolyte). An electrochemical stack may include one ofthese aforementioned units. An electrochemical stack may include severalof these aforementioned units arranged in electrical communication(e.g., serial or parallel electrical connection). In some examples, whenthe electrochemical stack includes several units, the units are layeredor laminated together in a column. In some examples, when theelectrochemical stack includes several units, the units are layered orlaminated together in an array. In some examples, when theelectrochemical stack includes several units, the stacks are arrangedsuch that one negative electrode is shared with two or more positiveelectrodes. Alternatively, in some examples, when the electrochemicalstack includes several units, the stacks are arranged such that onepositive electrode is shared with two or more negative electrodes.Unless specified otherwise, an electrochemical stack includes onepositive electrode, one solid electrolyte, and one negative electrode,and optionally includes a bonding layer between the positive electrodeand the solid electrolyte.

As used here, the phrase “positive electrode,” refers to the electrodein a secondary battery towards which positive ions, e.g., Li⁺, conduct,flow, or move during discharge of the battery. As used herein, thephrase “negative electrode” refers to the electrode in a secondarybattery from where positive ions, e.g., Li⁺, flow, or move duringdischarge of the battery. In a battery comprised of a Li-metal electrodeand a conversion chemistry, intercalation chemistry, or combinationconversion/intercalation chemistry-including electrode (i.e., cathodeactive material; e.g., NiF_(x), NCA, LiNi_(x)Mn_(y)Co_(z)O₂ [NMC] orLiNi_(x)Al_(y)Co_(z)O₂ [NCA], wherein x+y+z=1), the electrode having theconversion chemistry, intercalation chemistry, or combinationconversion/intercalation chemistry material is referred to as thepositive electrode. In some common usages, cathode is used in place ofpositive electrode, and anode is used in place of negative electrode.When a Li-secondary battery is charged, Li ions move from the positiveelectrode (e.g., NiF_(x), NMC, NCA) towards the negative electrode(e.g., Li-metal). When a Li-secondary battery is discharged, Li ionsmove towards the positive electrode and from the negative electrode.

As used herein, the term “surface roughness” refers to a measurement ofeither an arithmetic average of absolute values of sampled surfaceroughness amplitudes or a measurement of the maximum peak height ofsampled surface roughness amplitudes. As used herein, the term, “Ra,” isa measure of surface roughness wherein Ra is an arithmetic average ofabsolute values of sampled surface roughness amplitudes. Surfaceroughness measurements can be accomplished using, for example, a KeyenceVK-X100 instrument that measures surface roughness using a laser. Asused herein, the term, “Rt,” is a measure of surface roughness whereinRt is the maximum peak height of sampled surface roughness amplitudes.

As used herein, the term “roughened” refers to a surface that has adetermined surface roughness.

As used herein, the term “rational number” refers to any number whichcan be expressed as the quotient or fraction (e.g., p/q) of two integers(e.g., p and q), with the denominator (e.g., q) not equal to zero.Example rational numbers include, but are not limited to, 1, 1.1, 1.52,2, 2.5, 3, 3.12, and 7.

As used herein, voltage is set forth with respect to lithium (i.e., Vvs. Li) metal unless stated otherwise.

As used herein, “powder mixture decomposition temperature” refers to thetemperature at which the powder mixture starts to evolve hydrogen inappreciable rates so that the stoichiometry of the finished product ischanged by more than 1% with respect to its stoichiometry.

General Embodiments

Referring to the Drawing, FIG. 1 shows one embodiment of an energystorage device, generally designated 10. The energy storage deviceincludes a cathode 20, an anode 40, a solid-state ion conductor 30positioned between the positive electrode and the anode, and currentcollectors 50 and 60, corresponding to a positive electrode currentcollector 50 and an anode current collector 60, respectively. In thisembodiment, the solid-state ion conductor 30 may be an uncoated garnetconfigured to electrically insulate the positive electrode from theanode, while still allowing ion conduction (e.g., lithium ions) betweenthe positive electrode and the anode during operation of energy storagedevice 10.

Now referring to FIG. 2A, shown is another embodiment of an energystorage device 210. This embodiment also includes a cathode 220, ananode 240, a solid-state conductor 230 positioned between the positiveelectrode and the anode, and current collectors 250 and 260corresponding to a positive electrode current collector and an anodecurrent collector, respectively. In this embodiment, the solid-state ionconductor 230 may be configured as a coated garnet 230A, also configuredto electrically insulate the positive electrode from the anode, whilestill allowing ionic flow (e.g., lithium ions) between the positiveelectrode and the anode during operation of energy storage device 210.In this embodiment, a coating 230B may surround the coated garnet 230A.In an alternate embodiment, the coating 230B may be only or primarily onthe anode-side of separator 230A. In an alternate embodiment, thecoating 230B may be only or primarily on the cathode-side of separator 3A. Further, in this embodiment, cathode 220 includes a cathode-facingseparator 270 positioned between coating 230B and cathode 220. Forclarity purposes, cathode-facing separator 270 is depicted as a layer.In certain embodiments, however, catholyte 270 may penetrate, soak into,and/or be interspersed or infiltrate throughout cathode 220 while stillbeing positioned between cathode 220 and coating 230B, as in FIG. 2B.For example, in FIG. 2B, catholyte 270 may remain in contact with eachof the cathode 220 and the solid-state conductor 230. Interestingly,Applicants have unexpectedly observed improved performance of 210 due tothe reduced degradation or decomposition of solid-state ion conductor230 due to the presence of coating 230B. Alternatively stated, coating230B minimizes the reactions of coated garnet 230A with the anode 240,such as those involving lithium dendrites, under typical operatingconditions for energy storage device 210.

Referring now to FIG. 3, shown is another embodiment of an energystorage device 310. This embodiment also includes a cathode 320, ananode 340, a solid-state conductor 330 positioned between the cathode320 and the anode 340, and current collectors 350 and 360 correspondingto a cathode current collector and an anode current collector,respectively. In this embodiment, the solid-state ion conductor 330 maybe configured as a coated garnet 330A, also configured to electricallyinsulate the positive electrode from the anode, while still allowingionic flow (e.g., lithium ions) between the cathode 320 and the anode340 during operation of energy storage device 310. In this embodiment, acoating 30B may coat one portion of the coated garnet 330A. As in FIG.2A, cathode 320 also includes a catholyte 370 positioned betweensolid-state conductor 330 and cathode 320. In certain embodimentssimilar to FIG. 2B, catholyte 370 may penetrate, soak into, and/or beinterspersed or infiltrate cathode 320 while still being positionedbetween cathode 320 and solid-state conductor 330. In this embodiment,Applicants have also unexpectedly observed improved performance of 310due to the reduced degradation or decomposition of 330A due to thepresence of coating 330B. Alternatively stated, coating 330B minimizesreaction of coated garnet 330A with the anode 340 under typicaloperating conditions for energy storage device 310.

Compositions

In certain embodiments, coating 230B, as in FIG. 2A or 2B, or 330B, asin FIG. 3, may include a composition having A·(LiBH₄)·B·(LiX)·C·(LiNH₂)wherein X may be fluorine, bromine, chloride, iodine, or a combinationthereof, and wherein 0.1≤A≤3, 0.1≤B≤4.5, and 0≤C≤9. In one embodiment, Xmay be bromine, chlorine, iodine, or a combination thereof. In anotherembodiment, X may be iodine. In some embodiments, A is 0.1, 0.2, 0.3,0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7,1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0. Insome embodiments, B is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0,1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4,2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8,3.9, 4.0, 4.1, 4.2, 4.3, 4.4, or 4.5. In some embodiments, C is 0.0,0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4,1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8,2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2,4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6,5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0,7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9. 8.0, 8.1, 8.2, 8.3, 8.4,8.5, 8.6, 8.7, 8.8, 8.9, or 9.0.

In one embodiment, the composition may be 3LiBH₄·2LiI19 3LiNH₂. Inanother embodiment, the composition may be 3LiBH₄·4LiI·9LiNH₂.

In another embodiment, the composition may be 3LiBH₄·2LiCl·3LiNH₂. Inanother embodiment, the composition may be 3LiBH₄·4LiCl·9LiNH₂.

In another embodiment, the composition may be 3LiBH₄·2LiBr·3LiNH₂. Inanother embodiment, the composition may be 3LiBH₄·4LiBr·9LiNH₂.

In some embodiments, the composition may exist in different physicalstates. For example, in one embodiment, the composition may beamorphous. By way of further example, in one embodiment, the compositionmay be semi-crystalline. The composition can be made amorphous orsemi-crystalline by controlling the sintering profile, e.g., byadjusting the cooling rate after sintering.

In certain embodiments, the composition may impart an ionic conductivitybeneficial to the operation of the energy storage device 10, as in FIG.1, 210, as in FIG. 2A or 2B, or 310, as in FIG. 3. In one embodiment,the composition may include a lithium ion conductivity greater than1×10⁻⁷ S/cm at 60° C. By way of further example, in one embodiment, thecomposition may include a lithium ion conductivity greater than 1×10⁻⁶S/cm at 60° C. By way of further example, in one embodiment, thecomposition may include a lithium ion conductivity greater than 1×10⁻⁵S/cm at 60° C. By way of further example, in one embodiment, thecomposition may include a lithium ion conductivity greater than 1×10⁻⁴S/cm at 60° C. By way of further example, in one embodiment, the totaleffective lithium ion conductivity is greater than 10⁻⁴ S/cm at 60° C.By way of further example, in one embodiment, the total effectivelithium ion conductivity is greater than 8×10⁻⁴ S/cm at 60° C.

In certain embodiments, the LBHI composition may include grains. Grainstypically include a diameter or size and may be characterized by amedian size, as defined above. For example, in one embodiment, thecomposition may have a d₉₀ grain size of less than 20 μm. By way offurther example, in one embodiment, the composition may have a d₉₀ grainsize of less than 10 μm. By way of further example, in one embodiment,the composition may have a d₉₀ grain size of less than 5 μm. By way offurther example, in one embodiment, the composition may have a d₉₀ grainsize of less than 2 μm. By way of further example, in one embodiment,the composition may have a d₉₀ grain size of less than 1 μm.

In certain embodiments, the LBHI composition may exist as a film, asingle entity, or a pellet. For example, in one embodiment, thecomposition is a thin film. By way of further example, in oneembodiment, the composition is a monolith. By way of further example, inone embodiment, the composition is a pressed pellet.

In some embodiments, the LBHI composition may further include an oxide,a sulfide, a sulfide-halide, or an electrolyte. For example, in oneembodiment, the oxide may be selected from a lithium-stuffed garnetcharacterized by the formula Li_(x)La_(y)Zr_(Z)O_(t)·qAl₂O₃, wherein4<x<10, 1<y<4, 1<z<3, 6<t<14, 0≤q≤1. By way of further example, in oneembodiment, the composition includes an oxide with a coating of LBHI,where the oxide may be selected from a lithium-stuffed garnetcharacterized by the formula Li_(x)La_(y)Zr_(Z)O_(t)·qAl₂O₃, wherein4<x<10, 1<y<4, 1<z<3, 6<t<14, 0≤q≤1. By way of further example, in oneembodiment, the oxide may be selected from a lithium-stuffed garnetcharacterized by the formula Li_(a)La_(b)Zr_(c)Al_(d)Me″_(e)O_(f),wherein 5<a<8.5; 2<b<4; 0<c≤2.5; 0≤d<2; 0≤e<2, and 10<f<13 and Me″ is ametal selected from Nb, Ga, Ta, or combinations thereof. By way offurther example, in one embodiment, the composition includes an oxidewith a coating of LBHI, where the oxide may be selected from alithium-stuffed garnet characterized by the formulaLi_(a)La_(b)Zr_(c)Al_(d)Me″_(e)O_(f), wherein 5<a<8.5; 2<b<4; 0<c≤2.5;0≤d<2; 0≤e<2, and 10<f<13 and Me″ is a metal selected from Nb, Ga, Ta,or combinations thereof. By way of further example, in oneLi_(a)La_(b)Zr_(c)Al_(d)Me″_(e)O_(f) embodiment as above, Me″ is Nb. Byway of further example, in one Li_(a)La_(b)Zr_(c)Al_(d)Me″_(e)O_(f)embodiment as above, Me″ is Ga. By way of further example, in oneLi_(a)La_(b)Zr_(c)Al_(d)Me″_(e)O_(f) embodiment as above, Me″ is Ta. Byway of further example, in one Li_(a)La_(b)Zr_(c)Al_(d)Me″_(e)O_(f)embodiment as above, Me″ is Nb and Ga. By way of further example, in oneLi_(a)La_(b)Zr_(c)Al_(d)Me″_(e)O_(f) embodiment as above, Me″ is Nb andTa. By way of further example, in oneLi_(a)La_(b)Zr_(c)Al_(d)Me″_(e)O_(f) embodiment as above, Me″ is Ga andTa.

By way of further example, in one embodiment, the oxide is alithium-stuffed garnet oxide characterized by the formulaLi_(u)La_(v)Zr_(x)O_(y)·zAl₂O₃, wherein

u is a rational number from 4 to 8;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14; and

z is a rational number from 0.05 to 1;

wherein u, v, x, y, and z are selected so that the lithium-stuffedgarnet oxide is charge neutral.

By way of further example, in one embodiment, the composition includesan oxide with a coating of LBHI, where the oxide is a lithium-stuffedgarnet oxide characterized by the formulaLi_(u)La_(v)Zr_(x)O_(y).zAl₂O₃, wherein

u is a rational number from 4 to 8;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14; and

z is a rational number from 0.05 to 1;

wherein u, v, x, y, and z are selected so that the lithium-stuffedgarnet oxide is charge neutral.

By way of further example, in one embodiment, the oxide is alithium-stuffed garnet oxide characterized by the formulaLi_(u)La_(v)Zr_(x)O_(y)·zT₂O₅, wherein

u is a rational number from 4 to 10;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14; and

z is a rational number from 0 to 1;

wherein u, v, x, y, and z are selected so that the lithium-stuffedgarnet oxide is charge neutral.

By way of further example, in one embodiment, the composition includesan oxide with a coating of LBHI, where the oxide is a lithium-stuffedgarnet oxide characterized by the formula Li_(u)La_(v)Zr_(x)O_(y)·zT₂O₅,wherein

u is a rational number from 4 to 10;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14; and

z is a rational number from 0 to 1;

wherein u, v, x, y, and z are selected so that the lithium-stuffedgarnet oxide is charge neutral.

By way of further example, in one embodiment, the oxide is alithium-stuffed garnet oxide characterized by the formulaLi_(u)La_(v)Zr_(x)O_(y)·zNb₂O₅, wherein

u is a rational number from 4 to 10;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14; and

z is a rational number from 0 to 1;

wherein u, v, x, y, and z are selected so that the lithium-stuffedgarnet oxide is charge neutral.

By way of further example, in one embodiment, the composition includesan oxide with a coating of LBHI, where the oxide is a lithium-stuffedgarnet oxide characterized by the formulaLi_(u)La_(v)Zr_(x)O_(y)·zNb₂O₅, wherein

u is a rational number from 4 to 10;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14; and

z is a rational number from 0 to 1;

wherein u, v, x, y, and z are selected so that the lithium-stuffedgarnet oxide is charge neutral.

By way of further example, in one embodiment, the oxide is alithium-stuffed garnet oxide characterized by the formulaLi_(u)La_(v)Zr_(x)O_(y)·zGa₂O₃, wherein

u is a rational number from 4 to 10;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14; and

z is a rational number from 0 to 1;

wherein u, v, x, y, and z are selected so that the lithium-stuffedgarnet oxide is charge neutral.

By way of further example, in one embodiment, the composition includesan oxide with a coating of LBHI, where the oxide is a lithium-stuffedgarnet oxide characterized by the formulaLi_(u)La_(v)Zr_(x)O_(y)·zGa₂O₃, wherein

u is a rational number from 4 to 10;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14; and

z is a rational number from 0 to 1;

wherein u, v, x, y, and z are selected so that the lithium-stuffedgarnet oxide is charge neutral.

By way of further example, in one embodiment, the oxide is alithium-stuffed garnet oxide characterized by the formulaLi_(u)La_(v)Zr_(x)O_(y)·zT₂O₅.bAl₂O₃, wherein

u is a rational number from 4 to 10;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14; and

z is a rational number from 0 to 1;

b is a rational number from 0 to 1;

wherein z+b≤1

wherein u, v, x, y, and z are selected so that the lithium-stuffedgarnet oxide is charge neutral.

By way of further example, in one embodiment, the composition includesan oxide with a coating of LBHI, where the oxide is a lithium-stuffedgarnet oxide characterized by the formulaLi_(u)La_(v)Zr_(x)O_(y)·T₂O₅·bAl₂O₃, wherein

u is a rational number from 4 to 10;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14; and

z is a rational number from 0 to 1;

b is a rational number from 0 to 1;

wherein z+b≤1

wherein u, v, x, y, and z are selected so that the lithium-stuffedgarnet oxide is charge neutral.

By way of further example, in one embodiment, the oxide is alithium-stuffed garnet oxide characterized by the formulaLi_(u)La_(v)Zr_(x)O_(y).zNb₂O₅.bAl₂O₃, wherein

u is a rational number from 4 to 10;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14; and

z is a rational number from 0 to 1;

b is a rational number from 0 to 1;

wherein z+b≤1

wherein u, v, x, y, and z are selected so that the lithium-stuffedgarnet oxide is charge neutral.

By way of further example, in one embodiment, the composition includesan oxide with a coating of LBHI, where the oxide is a lithium-stuffedgarnet oxide characterized by the formulaLi_(u)La_(v)Zr_(x)O_(y)·zNb₂O₅]bAl₂O₃, wherein

u is a rational number from 4 to 10;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14; and

z is a rational number from 0 to 1;

b is a rational number from 0 to 1;

wherein z+b≤1

wherein u, v, x, y, and z are selected so that the lithium-stuffedgarnet oxide is charge neutral.

By way of further example, in one embodiment, the oxide is alithium-stuffed garnet oxide characterized by the formulaLi_(u)La_(v)Zr_(x)O_(y)·zGa₂O₃·bAl₂O₃, wherein

u is a rational number from 4 to 10;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14; and

z is a rational number from 0 to 1;

b is a rational number from 0 to 1;

wherein z+b≤1 and wherein u, v, x, y, and z are selected so that thelithium-stuffed garnet oxide is charge neutral.

By way of further example, in one embodiment, the composition includesan oxide with a coating of LBHI, where the oxide is a lithium-stuffedgarnet oxide characterized by the formulaLi_(u)La_(v)Zr_(x)O_(y)·zGa₂O₃·bAl₂O₃, wherein

u is a rational number from 4 to 10;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14; and

z is a rational number from 0 to 1;

b is a rational number from 0 to 1;

wherein z+b≤1 and wherein u, v, x, y, and z are selected so that thelithium-stuffed garnet oxide is charge neutral. By way of furtherexample, in one embodiment, the oxide is Li₆₄Ga_(0.2)La₃Zr₂O₁₂ where thesubscripts and molar coefficients in the empirical formula are based onthe quantities of raw materials initially batched to make the describedLi₆₄Ga_(0.2)La₃Zr₂O₁₂.

In certain embodiments, the lithium-stuffed garnetLi_(x)La_(y)Zr_(Z)O_(t).qAl₂O₃ may be doped with Nb, Ga, and/or Ta. Byway of further example, in one embodiment, the lithium-stuffed garnetLi_(x)La_(y)Zr_(Z)O_(t)·qAl₂O₃ may be doped with Nb, Ga, and Ta. By wayof further example, in one embodiment, the lithium-stuffed garnetLi_(x)La_(y)Zr_(Z)O_(t)·qAl₂O₃ may be doped with Nb, Ga, or Ta. By wayof further example, in one embodiment, the lithium-stuffed garnetLi_(x)La_(y)Zr_(Z)O_(t)·qAl₂O₃ may be doped with Nb. By way of furtherexample, in one embodiment, the lithium-stuffed garnetLi_(x)La_(y)Zr_(Z)O_(t)·qAl₂O₃ may be doped with Ga. By way of furtherexample, in one embodiment, the lithium-stuffed garnetLi_(x)La_(y)Zr_(Z)O_(t).qAl₂O₃ may be doped with Ta.

In some embodiments, the sulfide or sulfide-halide may be selected fromthe group consisting of LSS, SLOPS, LSTPS, SLOBS, LATS, and LPS+X,wherein X is selected from Cl, I, or Br. For example, in one embodiment,the sulfide or sulfide-halide may be LSS. By way of further example, inone embodiment, the sulfide or sulfide-halide may be SLOPS. By way offurther example, in one embodiment, the sulfide or sulfide-halide may beLSTPS. By way of further example, in one embodiment, the sulfide orsulfide-halide may be SLOBS. By way of further example, in oneembodiment, the sulfide or sulfide-halide may be LATS. By way of furtherexample, in one embodiment, the sulfide or sulfide-halide may be LPS+X,wherein X is selected from Cl, I, or Br. By way of further example, thesulfide or sulfide halide may be LPS+X where LPS+X may be LPSCl. By wayof further example, the sulfide or sulfide halide may be LPS+X whereLPS+X may be LPSBr. By way of further example, the sulfide or sulfidehalide may be LPS+X where LPS+X may be LPSI. By way of further example,the sulfide halide may be Li_(a)Si_(b)P_(c)S_(d)X_(e), wherein 8<a<12,1<b<3, 1<c<3, 8<d<14, and 0<X<1, wherein X is F, Cl, Br, or I. By way offurther example, in one embodiment, the sulfide halide may beLi_(a)Si_(b)P_(c)S_(d)X_(e), wherein 8<a<12, 1<b<3, 1<c<3, 8<d<14, and0<X<1, wherein X is F. By way of further example, in one embodiment, thesulfide halide may be Li_(a)Si_(b)P_(c)S_(d)X_(e), wherein 8<a<12,1<b<3, 1<c<3, 8<d<14, and 0<X<1, wherein X is Cl. By way of furtherexample, in one embodiment, the sulfide halide may beLi_(a)Si_(b)P_(c)S_(d)X_(e), wherein 8<a<12, 1<b<3, 1<c<3, 8<d<14, and0<X<1, wherein X is Br. By way of further example, in one embodiment,the sulfide halide may be Li_(a)Si_(b)P_(c)S_(d)X_(e), wherein 8<a<12,1<b<3, 1<c<3, 8<d<14, and 0<X<1, wherein X is I. By way of furtherexample, in one embodiment, the sulfide may beLi_(a)Si_(b)Sn_(c)P_(d)S_(e)O_(f), wherein 2≤a≤8, 0≤b≤1, 0≤c≤1, b+c=1,0.5≤d≤2.5, 4≤e≤12, and 0<f≤10. By way of further example, in oneembodiment, the sulfide may be Li_(g)As_(h)Sn_(j)S_(k)O_(l), wherein2≤g≤6, 0≤h≤1, 0≤j≤1, 2≤k≤6, and 0≤l≤10. By way of further example, inone embodiment, the sulfide may be Li_(m)P_(n)S_(p)X_(q), wherein X═Cl,Br, and/or I, 2≤m≤6, 0≤n≤1, 0≤p≤1, and 2≤q≤6. By way of further example,in one embodiment, the sulfide may be Li_(m)P_(n)S_(p)I_(q), 2≤m≤6,0≤n≤1, 0≤p≤1, and 2≤q≤6. By way of further example, in one embodiment,the sulfide may be a mixture of (Li₂S):(P₂S₅) having a molar ratio fromabout 10:1 to about 6:4 and LiI, wherein the ratio of[(Li₂S):(P₂S₅)]:LiI is from 95:5 to 50:50. By way of further example, inone embodiment, the sulfide may be LPS+X, wherein X is selected from Cl,I, or Br. By way of further example, in one embodiment, the sulfide maybe vLi₂S+wP₂S₅+yLiX wherein coefficients v, w, and y are rationalnumbers from 0 to 1. By way of further example, in one embodiment, thesulfide may be vLi₂S+wSiS₂+yLiX wherein coefficients v, w, and y arerational numbers from 0 to 1. By way of further example, in oneembodiment, the sulfide may be vLi₂S+wSiS₂+yLiX wherein coefficients v,w, and y are rational numbers from 0 to 1. By way of further example, inone embodiment, the sulfide may be vLi₂S+wB₂S₃+yLiX wherein coefficientsv, w, and y are rational numbers from 0 to 1. By way of further example,in one embodiment, the sulfide may be vLi₂S+wB₂S₃+yLiX whereincoefficients v, w, and y are rational numbers from 0 to 1.

In some embodiments, the LBHI extends into the surface cavities of thesulfide-halide. In some embodiments, the LBHI coats the surface cavitiesof the sulfide-halide.

In some embodiments, the LBHI extends into the surface cavities of thelithium-stuffed garnet. In some embodiments, the LBHI coats the surfacecavities of the lithium-stuffed garnet.

In some embodiments, the electrolyte may be selected from the groupconsisting of: a mixture of LiI and Al₂O₃; Li₃N; LIRAP; LATP; LAGP; amixture of LiBH₄ and LiX wherein X is selected from Cl, I, or Br; andvLiBH₄+wLiX+yLiNH₂, wherein X is selected from Cl, I, or Br; whereincoefficients v, w, and y are rational numbers from 0 to 1. For example,in one embodiment, the electrolyte may be a mixture of LiI and Al₂O₃,Li₃N, LIRAP, a mixture of LiBH₄ and LiX wherein X is selected from Cl,I, or Br, or vLiBH₄+wLiX+yLiNH₂ wherein X is selected from Cl, I, or Brand wherein coefficients v, w, and y are rational numbers from 0 to 1.

In certain embodiments, the composition may include a lithiuminterfacial area-specific resistance. For example, in one embodiment,the lithium interfacial area-specific resistance is less than 20 Ωcm² at25° C.

In certain embodiments, the composition may further include atransmission coefficient at a particular incident wavelength. Forexample, in one embodiment, the composition has a transmissioncoefficient of greater than 0.05 at 500 nm incident wavelength. Inanother embodiment, the composition may also include transmissionproperties that vary by less than a percentage over a surface area ofthe composition. For example, in one embodiment, the composition has atransmission coefficient of greater than 0.05 at 500 nm incidentwavelength and the transmission properties of the composition vary byless than 50% over a surface area of at least 100 μm². In anotherembodiment, the composition may have a transmission coefficient orgreater than 0.05 at 500 nm incident wavelength and the composition isless than 1 mm thick.

Referring again to FIG. 2A, 2B, or 3, in certain embodiments, asolid-state ion conductor composition 230 or 330 may include alithium-stuffed garnet 230A or 330A, as described elsewhere herein, anda composition 230B or 330A having A·(LiBH₄)·B·(LiX)·C·(LiNH₂) or alithium borohydride (LBH), as described elsewhere herein, where the LBHIcoats a surface of the lithium-stuffed garnet. Typically, during theoperation of an energy storage device, lithium tends to plate outunevenly, or form lithium dendrites, onto surfaces with defects. Uponlithium dendrite formation, lithium also tends to cause energy storagedevice failures in the form of shorting. Applicants have unexpectedlyobserved that LBHI coating compositions provided herein remove or fillsurface defects by coating the defects, thereby extending the lifetimesfor energy storage devices. For example, in one embodiment, the LBHI maybe conformally bonded to the surface of the lithium-stuffed garnet. Byway of further example, in one embodiment, the LBHI may be bonded todefects in the lithium-stuffed garnet.

Referring again to FIG. 2A, 2B, or 3, in certain embodiments, asolid-state ion conductor composition 230 or 330 may include alithium-stuffed garnet 230A or 330A, as described elsewhere herein, anda composition 230B or 330A having A·(LiBH₄)·B·(LiX)·C·(LiNH₂) or alithium borohydride (LBH), as described elsewhere herein, where the LBHIcoats a surface of the lithium-stuffed garnet. Typically, during theoperation of an energy storage device, lithium tends to plate outunevenly, or form lithium dendrites, onto surfaces with defects. Uponlithium dendrite formation, lithium also tends to cause energy storagedevice failures in the form of shorting. Applicants have unexpectedlyobserved that coating comprising A·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein Xis fluorine (F), bromine (Br), chloride (CO, iodine (I), or acombination thereof, and wherein 0.1<≤A≤4, 0.1≤B≤4, and 0≤C≤9, providedherein remove or fill surface defects by coating the defects, therebyextending the lifetimes for energy storage devices. For example, in oneembodiment, the LBHI may be conformally bonded to the surface of thelithium-stuffed garnet. By way of further example, in one embodiment,the LBHI may be bonded to defects in the lithium-stuffed garnet.

In some examples, including any of the foregoing, the compositionincludes A·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X may be fluorine, bromine,chloride, iodine, or a combination thereof, and wherein 0.1≤A≤4.5,0.1≤B≤4.5, and 0≤C≤9. In one embodiment, X may be bromine, chlorine,iodine, or a combination thereof. In another embodiment, X may beiodine. In some embodiments, A is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7,0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1,2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.03.1, 3.2, 3.3, 3.4, 3.5, 3.6,3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, or 4.5. In some embodiments, Bis 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4,1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8,2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2,4.3, 4.4, or 4.5. In some embodiments, C is 0.0, 0.1, 0.2, 0.3, 0.4,0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8,1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2,3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6,4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0,6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4,7.5, 7.6, 7.7, 7.8, 7.9. 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8,8.9, or 9.0. In some examples, including any of the foregoing, thecomposition includes a lithium-stuffed garnet. In some examples,including any of the foregoing, the composition is a thin film. In someexamples, including any of the foregoing, the composition is a pellet.

Composition Dimensions

In some embodiments, the LBHI composition may be a film (e.g., on acurrent collector such as copper metal or on an electrolyte such aslithium-stuffed garnet monoliths or thin films). For example, in oneembodiment, the composition may be a thin film. In certain embodiments,the thin films set forth herein have a thickness greater than 10 nm andless than 30 μm. For example, in one embodiment, the thin films are lessthan 20 μm in thickness. By way of further example, in one embodiment,the thin films are less than 19 μm in thickness. By way of furtherexample, in one embodiment, the thin films are less than 18 μm inthickness. By way of further example, in one embodiment, the thin filmsare less than 17 μm in thickness. By way of further example, in oneembodiment, the thin films are less than 16 μm in thickness. By way offurther example, in one embodiment, the thin films are less than 15 μmin thickness. By way of further example, in one embodiment, the thinfilms are less than 14 μm in thickness. By way of further example, inone embodiment, the thin films are less than 13 μm in thickness. By wayof further example, in one embodiment, the thin films are less than 12μm in thickness. By way of further example, in one embodiment, the thinfilms are less than 11 μm in thickness. By way of further example, inone embodiment, the thin films are less than 10 μm in thickness. By wayof further example, in one embodiment, the thin films are less than 9 μmin thickness. By way of further example, in one embodiment, the thinfilms are less than 8 μm in thickness. By way of further example, in oneembodiment, the thin films are less than 7 μm in thickness. By way offurther example, in one embodiment, the thin films are less than 6 μm inthickness. By way of further example, in one embodiment, the thin filmsare less than 5 μm in thickness. By way of further example, in oneembodiment, the thin films are less than 4 μm in thickness. By way offurther example, in one embodiment, the thin films are less than 3 μm inthickness. By way of further example, in one embodiment, the thin filmsare less than 2 μm in thickness. By way of further example, in oneembodiment, the thin films are less than 1 μm in thickness. By way offurther example, in one embodiment, the thin films are at least 1 nm inthickness.

In some embodiments, the composition comprisingA·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X is fluorine (F), bromine (Br),chloride (CO, iodine (I), or a combination thereof, and wherein0.1<≤A≤4, 0.1<≤B≤4, and 0≤C≤9 may be a film (e.g., on a currentcollector such as copper metal or on an electrolyte such aslithium-stuffed garnet monoliths or thin films). For example, in oneembodiment, the composition may be a thin film. In certain embodiments,the thin films set forth herein have a thickness greater than 10 nm andless than 30 μm. For example, in one embodiment, the thin films are lessthan 20 μm in thickness. By way of further example, in one embodiment,the thin films are less than 19 μm in thickness. By way of furtherexample, in one embodiment, the thin films are less than 18 μm inthickness. By way of further example, in one embodiment, the thin filmsare less than 17 μm in thickness. By way of further example, in oneembodiment, the thin films are less than 16 μm in thickness. By way offurther example, in one embodiment, the thin films are less than 15 μmin thickness. By way of further example, in one embodiment, the thinfilms are less than 14 μm in thickness. By way of further example, inone embodiment, the thin films are less than 13 μm in thickness. By wayof further example, in one embodiment, the thin films are less than 12μm in thickness. By way of further example, in one embodiment, the thinfilms are less than 11 μm in thickness. By way of further example, inone embodiment, the thin films are less than 10 μm in thickness. By wayof further example, in one embodiment, the thin films are less than 9 μmin thickness. By way of further example, in one embodiment, the thinfilms are less than 8 μm in thickness. By way of further example, in oneembodiment, the thin films are less than 7 μm in thickness. By way offurther example, in one embodiment, the thin films are less than 6 μm inthickness. By way of further example, in one embodiment, the thin filmsare less than 5 μm in thickness. By way of further example, in oneembodiment, the thin films are less than 4 μm in thickness. By way offurther example, in one embodiment, the thin films are less than 3 μm inthickness. By way of further example, in one embodiment, the thin filmsare less than 2 μm in thickness. By way of further example, in oneembodiment, the thin films are less than 1 μm in thickness. By way offurther example, in one embodiment, the thin films are at least 1 nm inthickness.

In some of these examples, including any of the foregoing, the films are1 mm in length. In some other of these examples, the films are 5 mm inlength. In yet other examples, the films are 10 mm in length. In stillother examples, the films are 15 mm in length. In certain examples, thefilms are 25 mm in length. In other examples, the films are 30 mm inlength. In some examples, the films are 35 mm in length. In some otherexamples, the films are 40 mm in length. In still other examples, thefilms are 45 mm in length. In certain examples, the films are 50 mm inlength. In other examples, the films are 30 mm in length. In someexamples, the films are 55 mm in length. In some other examples, thefilms are 60 mm in length. In yet other examples, the films are 65 mm inlength. In still other examples, the films are 70 mm in length. Incertain examples, the films are 75 mm in length. In other examples, thefilms are 80 mm in length. In some examples, the films are 85 mm inlength. In some other examples, the films are 90 mm in length. In stillother examples, the films are 95 mm in length. In certain examples, thefilms are 100 mm in length. In other examples, the films are 30 mm inlength.

In some examples, the films are 1 cm in length. In some other examples,the films are 2 cm in length. In other examples, the films are 3 cm inlength. In yet other examples, the films are 4 cm in length. In someexamples, the films are 5 cm in length. In other examples, the films are6 cm in length. In yet other examples, the films are 7 cm in length. Insome other examples, the films are 8 cm in length. In yet otherexamples, the films are 9 cm in length. In still other examples, thefilms are 10 cm in length. In some examples, the films are 11 cm inlength. In some other examples, the films are 12 cm in length. In otherexamples, the films are 13 cm in length. In yet other examples, thefilms are 14 cm in length. In some examples, the films are 15 cm inlength. In other examples, the films are 16 cm in length. In yet otherexamples, the films are 17 cm in length. In some other examples, thefilms are 18 cm in length. In yet other examples, the films are 19 cm inlength. In still other examples, the films are 20 cm in length. In someexamples, the films are 21 cm in length. In some other examples, thefilms are 22 cm in length. In other examples, the films are 23 cm inlength. In yet other examples, the films are 24 cm in length. In someexamples, the films are 25 cm in length. In other examples, the filmsare 26 cm in length. In yet other examples, the films are 27 cm inlength. In some other examples, the films are 28 cm in length. In yetother examples, the films are 29 cm in length. In still other examples,the films are 30 cm in length. In some examples, the films are 31 cm inlength. In some other examples, the films are 32 cm in length. In otherexamples, the films are 33 cm in length. In yet other examples, thefilms are 34 cm in length. In some examples, the films are 35 cm inlength. In other examples, the films are 36 cm in length. In yet otherexamples, the films are 37 cm in length. In some other examples, thefilms are 38 cm in length. In yet other examples, the films are 39 cm inlength. In still other examples, the films are 40 cm in length. In someexamples, the films are 41 cm in length. In some other examples, thefilms are 42 cm in length. In other examples, the films are 43 cm inlength. In yet other examples, the films are 44 cm in length. In someexamples, the films are 45 cm in length. In other examples, the filmsare 46 cm in length. In yet other examples, the films are 47 cm inlength. In some other examples, the films are 48 cm in length. In yetother examples, the films are 49 cm in length. In still other examples,the films are 50 cm in length. In some examples, the films are 51 cm inlength. In some other examples, the films are 52 cm in length. In otherexamples, the films are 53 cm in length. In yet other examples, thefilms are 54 cm in length. In some examples, the films are 55 cm inlength. In other examples, the films are 56 cm in length. In yet otherexamples, the films are 57 cm in length. In some other examples, thefilms are 58 cm in length. In yet other examples, the films are 59 cm inlength. In still other examples, the films are 60 cm in length. In someexamples, the films are 61 cm in length. In some other examples, thefilms are 62 cm in length. In other examples, the films are 63 cm inlength. In yet other examples, the films are 64 cm in length. In someexamples, the films are 65 cm in length. In other examples, the filmsare 66 cm in length. In yet other examples, the films are 67 cm inlength. In some other examples, the films are 68 cm in length. In yetother examples, the films are 69 cm in length. In still other examples,the films are 70 cm in length. In some examples, the films are 71 cm inlength. In some other examples, the films are 72 cm in length. In otherexamples, the films are 73 cm in length. In yet other examples, thefilms are 74 cm in length. In some examples, the films are 75 cm inlength. In other examples, the films are 76 cm in length. In yet otherexamples, the films are 77 cm in length. In some other examples, thefilms are 78 cm in length. In yet other examples, the films are 79 cm inlength. In still other examples, the films are 80 cm in length. In someexamples, the films are 81 cm in length. In some other examples, thefilms are 82 cm in length. In other examples, the films are 83 cm inlength. In yet other examples, the films are 84 cm in length. In someexamples, the films are 85 cm in length. In other examples, the filmsare 86 cm in length. In yet other examples, the films are 87 cm inlength. In some other examples, the films are 88 cm in length. In yetother examples, the films are 89 cm in length. In still other examples,the films are 90 cm in length. In some examples, the films are 91 cm inlength. In some other examples, the films are 92 cm in length. In otherexamples, the films are 93 cm in length. In yet other examples, thefilms are 94 cm in length. In some examples, the films are 95 cm inlength. In other examples, the films are 96 cm in length. In yet otherexamples, the films are 97 cm in length. In some other examples, thefilms are 98 cm in length. In yet other examples, the films are 99 cm inlength. In still other examples, the films are 100 cm in length. In someexamples, the films are 101 cm in length. In some other examples, thefilms are 102 cm in length. In other examples, the films are 103 cm inlength. In yet other examples, the films are 104 cm in length. In someexamples, the films are 105 cm in length. In other examples, the filmsare 106 cm in length. In yet other examples, the films are 107 cm inlength. In some other examples, the films are 108 cm in length. In yetother examples, the films are 109 cm in length. In still other examples,the films are 110 cm in length. In some examples, the films are 111 cmin length. In some other examples, the films are 112 cm in length. Inother examples, the films are 113 cm in length. In yet other examples,the films are 114 cm in length. In some examples, the films are 115 cmin length. In other examples, the films are 116 cm in length. In yetother examples, the films are 117 cm in length. In some other examples,the films are 118 cm in length. In yet other examples, the films are 119cm in length. In still other examples, the films are 120 cm in length.

In some examples, the garnet-based films are prepared as a monolithuseful for a lithium secondary battery cell. In some of these cells, theform factor for the garnet-based film is a film with a top surface areaof about 10 cm². In certain cells, the form factor for the garnet-basedfilm with a top surface area of about 25 cm². In certain cells, the formfactor for the garnet-based film with a top surface area of about 100cm². In certain cells, the form factor for the garnet-based film with atop surface area of about 200 cm².

In some examples, the films set forth herein have a Young's Modulus ofabout 130-150 GPa. In some other examples, the films set forth hereinhave a Vicker's hardness of about 5-7 GPa. In some other examples, thefilms set forth herein have a fracture strength of greater than 300 MPaor greater than 400 MPa or greater than 500 MPa, or greater than 600MPa, or greater than 700 MPa, or greater than 800 MPa, or greater than900 MPa, or greater than 1 GPa. In some of these examples, the filmsinclude a lithium-stuffed garnet. In some of these examples, the filmsinclude a lithium-stuffed garnet coated with LBHI.

In certain embodiments, the composition may be a thin film and include aporosity as determined by SEM for the thin film. For example, in oneembodiment, the compositions set forth herein may have a porosity lessthan 5%. By way of further example, in one embodiment, the compositionsset forth herein may have a porosity less than 6%. By way of furtherexample, in one embodiment, the compositions set forth herein may have aporosity less than 7%. By way of further example, in one embodiment, thecompositions set forth herein may have a porosity less than 8%. By wayof further example, in one embodiment, the compositions set forth hereinmay have a porosity less than 4%. By way of further example, in oneembodiment, the compositions set forth herein may have a porosity lessthan 3%. By way of further example, in one embodiment, the compositionsset forth herein may have a porosity less than 2%. By way of furtherexample, in one embodiment, the compositions set forth herein may have aporosity less than 1%. By way of further example, in one embodiment, thecompositions set forth herein may have a porosity less than 0.5%.

In certain embodiments, the composition may be a thin film and include aporosity as determined by SEM for the thin film. For example, in oneembodiment, the compositions set forth herein may have a porosity lessthan 5% by volume. By way of further example, in one embodiment, thecompositions set forth herein may have a porosity less than 6% byvolume. By way of further example, in one embodiment, the compositionsset forth herein may have a porosity less than 7% by volume. By way offurther example, in one embodiment, the compositions set forth hereinmay have a porosity less than 8% by volume. By way of further example,in one embodiment, the compositions set forth herein may have a porosityless than 4% by volume. By way of further example, in one embodiment,the compositions set forth herein may have a porosity less than 3% byvolume. By way of further example, in one embodiment, the compositionsset forth herein may have a porosity less than 2% by volume. By way offurther example, in one embodiment, the compositions set forth hereinmay have a porosity less than 1% by volume. By way of further example,in one embodiment, the compositions set forth herein may have a porosityless than 0.5% by volume.

In certain embodiments, substrates having thin films deposited thereonmay be prepared via dip coating. Applicants have unexpectedly noted thatdip coating the substrate to express thin films improves the surface ofthe substrate. For example, in one embodiment, the surface of thesubstrate may have a smooth surface. Dip coatings may include aplurality of dips. For example, in one embodiment, a substrate may bedip coated 1 time. By way of further example, a substrate may be dipcoated 2 times. By way of further example, a substrate may be dip coated5 times. By way of further example, a substrate may be dip coated 10times. By way of further example, a substrate may be dip coated 20times.

Dip coating typically includes a withdrawal rate that affects thethickness of the coating. In certain embodiments the withdrawal rate mayinclude a range of 0.01 to 0.25 mm/min. For example, in one embodiment,the withdrawal rate is 0.05 mm/min. By way of further example, in oneembodiment, the withdrawal rate is 0.1 mm/min. By way of furtherexample, in one embodiment, the withdrawal rate is 0.15 mm/min. By wayof further example, in one embodiment, the withdrawal rate is 0.2mm/min. By way of further example, in one embodiment, the withdrawalrate is 0.25 mm/min. Withdrawal rate may be determined, for example, bymeasuring the distance of a substrate out of a molt per time.

In certain embodiments, the thin film coating thickness may be governedby the Landau-Levich equation shown below:

$h = \frac{0.94\left( {\eta\; U} \right)^{2/3}}{{\gamma_{LV}^{1/6}\left( {\rho\; g} \right)}^{1/2}}$where h is the coating thickness, η is the viscosity, U is withdrawalrate or wall speed, γ_(LV) is the liquid-vapor surface tension, ρ is thedensity, and g is gravity. Coating thickness is largely determined bythe withdrawal rate, solid content, and viscosity of the liquid. Incertain embodiments, the thin film coating may not be governed by theLandau-Levich equation. For example, in one embodiment, a withdrawalrate of about 0.1 mm/min provides a film thickness of about 70 μm. Byway of further example, in one embodiment, a withdrawal rate of <0.1mm/min provides a film thickness of about 1 μm to about 10 μm. By way offurther example, in one embodiment, a withdrawal rate of <0.1 mm/min anda retention time of about 5 min to about 10 min provides a filmthickness of about 1 μm to about 10 μm.

In certain embodiments, the combination of multiple dips via dip coatingproduces a smooth film. For example, in one embodiment, 2-5 dips may beused. By way of further example, in one embodiment, 5-15 dips may beused. By way of further example, in one embodiment, 2-20 dips may beused. By way of further example, in one embodiment, 10-30 dips may beused.

For example, in one embodiment, dip coating at >4 mm/sec provides asmooth film. By way of further example, in one embodiment, dip coatingat >4 mm/sec with a thermal equilibration time of about 5 s to about 20s provides a smooth film. By way of further example, in one embodiment,dip coating at >4 mm/sec with a thermal equilibration time of about 5 sto about 20 s and dip cycling about 10 to about 30 times provides asmooth film. By way of further example, in one embodiment, dip coatingat >4 mm/sec with a thermal equilibration time of about 5 s to about 20s with dip cycling about 10 to about 30 times and a total retention timeof about 200 s provides a smooth film. By way of further example, in oneembodiment, dip coating at >4 mm/sec with a thermal equilibration timeof about 5 s to about 20 s at 330-384° C. with dip cycling about 10 toabout 30 times and a total retention time of about 6.7 min provides asmooth film.

In certain embodiments, the molten LBHXN is applied via spin coating. Aspin coater with heating capability is used for this embodiment. Powderis first applied on the substrate to be coated. The spin coater isheated to or above the melting point of the LBHXN. After melting, thesubstrate is rotated at speed of 100-5000 rpm while heat is applied. Itis to be understood that the spin speed may correlate strongly with thecoating film thickness. After rotation stops, the 2nd layer, which couldbe a solid-state cathode film, or another lithium ion conductingseparator (which is the same or a different Li ion conductor than thefirst substrate) is laminated at a pressure of 10-2000 pounds per squareinch (PSI). Heat is optionally applied. After cooling the laminate toroom temperature, the substrate, LBHXN and top layer are bonded togethervery well and cannot be separated without breaking.

Energy Storage Devices

In some embodiments, the disclosure herein sets forth energy storagedevices 10 including electrochemical cells, as described elsewhereherein. For example, in one embodiment, an electrochemical cell includesa positive electrode, a negative electrode and a solid-state electrolytehaving the composition as described any of the foregoing examples orembodiments, or any others set forth herein. By way of further example,in one embodiment, the electrochemical cell is a rechargeable battery.

Battery Architectures

Referring again to FIG. 3, shown is another embodiment of an energystorage device or electrochemical cell 310. This embodiment alsoincludes a positive electrode or cathode 320, an anode or lithium metalnegative electrode 340, a solid-state conductor or solid separator 330positioned between the cathode 320 and the anode 340, and currentcollectors 350 and 360 corresponding to a cathode current collector andan anode current collector, respectively. In this embodiment, the solidseparator 330 may be configured as a coated garnet 330A, also includinga cathode directly contacting the separator and an anode directlycontacting the separator further configured to electrically insulate thecathode from the anode, while still allowing ionic flow (e.g., lithiumions) between the cathode 320 and the anode 340 during operation ofenergy storage device 310. In this embodiment, the anode directlycontacts the separator 330, where coating 330B may coat one portion ofthe solid separator 330. Again, as in FIG. 2, cathode 220 also includesa catholyte 270 positioned between solid separator 230 and cathode 220.In certain embodiments, catholyte 270 may penetrate cathode 220 whilestill being positioned between cathode 220 and solid separator 230, asin FIG. 2A. Further, in this embodiment, the anode directly contactingthe separator 230B includes the composition(s) as described elsewhereherein. In another embodiment, the anode directly contacting theseparator 230B may be less than 20 μm thick.

In another embodiment, the solid separator 230 may be configured as acoated garnet 230A, also including a cathode-interfacing separatorand/or an anode-interfacing separator further configured to electricallyinsulate the cathode from the anode, while still allowing ionic flow(e.g., lithium ions) between the cathode 220 and the anode 240 duringoperation of energy storage device 210. For example, in certainembodiments, the cathode-interfacing separator may not directly contactthe separator. By way of further example, in certain embodiments, theanode-interfacing separator may not directly contact the separator.

Methods of Making the Materials Described Herein

In certain embodiments, disclosed herein is a method for making a thinfilm including the A·(LiBH₄)·B·(LiX)·C·(LiNH₂) composition, the methodincluding a) preparing a A·(LiBH₄)·B·(LiX)·C·(LiNH₂) compositionmaterial, b) providing a molten mixture, wherein the mixture includesA·(LiBH₄)·B·(LiX)·C·(LiNH₂), wherein X is fluorine, bromine, chlorine,iodine, or a combination thereof, and wherein 0.1≤A≤3, 0.1≤B≤4, and0≤C≤9; c) dip-coating a substrate in the molten mixture; d) withdrawingthe substrate; and e) cooling the substrate to room temperature. In someexamples, the substrate is a current collector. In some examples, thesubstrate is a solid electrolyte. In some examples, the substrate is alithium-stuffed garnet.

In certain embodiments, the thin films of LBHI set forth from the methodherein have a thickness greater than 10 nm and less than 30 μm. Forexample, in one embodiment, the thin films set forth from the method areless than 20 μm in thickness. By way of further example, in oneembodiment, the thin films set forth from the method are less than 19 μmin thickness. By way of further example, in one embodiment, the thinfilms set forth from the method are less than 18 μm in thickness. By wayof further example, in one embodiment, the thin films set forth from themethod are less than 17 μm in thickness. By way of further example, inone embodiment, the thin films set forth from the method are less than16 μm in thickness. By way of further example, in one embodiment, thethin films set forth from the method are less than 15 μm in thickness.By way of further example, in one embodiment, the thin films set forthfrom the method are less than 14 μm in thickness. By way of furtherexample, in one embodiment, the thin films set forth from the method areless than 13 μm in thickness. By way of further example, in oneembodiment, the thin films set forth from the method are less than 12 μmin thickness. By way of further example, in one embodiment, the thinfilms set forth from the method are less than 11 μm in thickness. By wayof further example, in one embodiment, the thin films set forth from themethod are less than 10 μm in thickness. By way of further example, inone embodiment, the thin films set forth from the method are less than 9μm in thickness. By way of further example, in one embodiment, the thinfilms set forth from the method are less than 8 μm in thickness. By wayof further example, in one embodiment, the thin films set forth from themethod are less than 7 μm in thickness. By way of further example, inone embodiment, the thin films set forth from the method are less than 6μm in thickness. By way of further example, in one embodiment, the thinfilms set forth from the method are less than 5 μm in thickness. By wayof further example, in one embodiment, the thin films set forth from themethod are less than 4 μm in thickness. By way of further example, inone embodiment, the thin films set forth from the method are less than 3μm in thickness. By way of further example, in one embodiment, the thinfilms set forth from the method are less than 2 μm in thickness. By wayof further example, in one embodiment, the thin films set forth from themethod are less than 1 μm in thickness. In certain embodiments, the LBHImaterial may penetrate pores of the separator and may not be itselfdistinguishable as a separate layer.

In certain embodiments, the method may impart an ionic conductivitybeneficial to the operation of the energy storage device 10, 210, or310. For example, ionic conductivity may be for ions such as lithium. Byway of further example, in one embodiment, the method may impart alithium ion conductivity greater than 1×10⁻⁷ S/cm at 60° C. By way offurther example, in one embodiment, the method may impart a lithium ionconductivity greater than 1×10⁻⁶ S/cm at 60° C. By way of furtherexample, in one embodiment, the method may impart a lithium ionconductivity greater than 1×10⁻⁵ S/cm at 60° C. By way of furtherexample, in one embodiment, the method may impart a lithium ionconductivity greater than 1×10⁻⁴ S/cm at 60° C. By way of furtherexample, in one embodiment, the method may impart a lithium ionconductivity greater than 8×10⁻⁴ S/cm at 60° C. Ion conductivity may bedetermined, for example, indirectly from the impedance in ASRmeasurements described elsewhere herein.

In certain embodiments, the substrate in the method may be a solidseparator-electrolyte for a lithium battery. For example, in oneembodiment, the substrate in the method may be a solidseparator-electrolyte garnet for a lithium battery. By way of furtherexample, in one embodiment, the substrate in the method may be a metalselected from the group consisting of copper and nickel. By way offurther example, in one embodiment, the substrate in the method may becopper. By way of further example, in one embodiment, the substrate inthe method may be nickel. By way of further example, in one embodiment,the substrate in the method may be a foil. By way of further example, inone embodiment, the substrate in the method may be a LPSI. By way offurther example, in one embodiment, the substrate in the method may be aLPSI composite.

In certain embodiments, provided herein is a composite having alithium-stuffed garnet and an LBHI, where the LBHI fills at least 90% ofthe through-pores and/or surface pores of the lithium-stuffed garnet,and where the LBHI may be a composition havingA·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X is a halide. In certainembodiments, provided herein is a composite having a lithium-stuffedgarnet and an LBHI, where the LBHI fills at least 95% of thethrough-pores and/or surface pores of the lithium-stuffed garnet, andwhere the LBHI may be a composition having A·(LiBH₄)·B (LiX)·C·(LiNH₂)wherein X is a halide wherein 0.1≤A≤4, 0.1≤B≤4, and 0≤C≤9.

In certain embodiments, provided herein is a composite having alithium-stuffed garnet and an LBHI, where the LBHI fills at least 95% ofthe through-pores and/or surface pores of the lithium-stuffed garnet,and where the LBHI may be a composition havingA·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X is a halide wherein 0.1≤A≤4,0.1≤B≤4, and 0≤C≤9.

In certain embodiments, provided herein is a composite having alithium-stuffed garnet and an LBHI, where the LBHI fills at least 90% ofthe through-pores and/or surface pores of the lithium-stuffed garnet,and where the LBHI may be a composition havingA·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X is a halide wherein 0.1≤A≤4,0.1≤B≤4, and 0≤C≤9.

In certain embodiments, provided herein is a composite having alithium-stuffed garnet and an LBHI, where the LBHI fills at least 91% ofthe through-pores and/or surface pores of the lithium-stuffed garnet,and where the LBHI may be a composition havingA·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X is a halide wherein 0.1≤A≤4,0.1≤B≤4, and 0≤C≤9.

In certain embodiments, provided herein is a composite having alithium-stuffed garnet and an LBHI, where the LBHI fills at least 92% ofthe through-pores and/or surface pores of the lithium-stuffed garnet,and where the LBHI may be a composition havingA·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X is a halide wherein 0.1≤A≤4,0.1≤B≤4, and 0≤C≤9.

In certain embodiments, provided herein is a composite having alithium-stuffed garnet and an LBHI, where the LBHI fills at least 93% ofthe through-pores and/or surface pores of the lithium-stuffed garnet,and where the LBHI may be a composition havingA·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X is a halide wherein 0.1≤A≤4,0.1≤B≤4, and 0≤C≤9.

In certain embodiments, provided herein is a composite having alithium-stuffed garnet and an LBHI, where the LBHI fills at least 94% ofthe through-pores and/or surface pores of the lithium-stuffed garnet,and where the LBHI may be a composition havingA·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X is a halide wherein 0.1≤A≤4,0.1≤B≤4, and 0≤C≤9.

In certain embodiments, provided herein is a composite having alithium-stuffed garnet and an LBHI, where the LBHI fills at least 95% ofthe through-pores and/or surface pores of the lithium-stuffed garnet,and where the LBHI may be a composition havingA·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X is a halide wherein 0.1≤A≤4,0.1≤B≤4, and 0≤C≤9.

In certain embodiments, provided herein is a composite having alithium-stuffed garnet and an LBHI, where the LBHI fills at least 96% ofthe through-pores and/or surface pores of the lithium-stuffed garnet,and where the LBHI may be a composition havingA·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X is a halide wherein 0.1≤A≤4,0.1≤B≤4, and 0≤C≤9.

In certain embodiments, provided herein is a composite having alithium-stuffed garnet and an LBHI, where the LBHI fills at least 97% ofthe through-pores and/or surface pores of the lithium-stuffed garnet,and where the LBHI may be a composition havingA·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X is a halide wherein 0.1≤A≤4,0.1≤B≤4, and 0≤C≤9.

In certain embodiments, provided herein is a composite having alithium-stuffed garnet and an LBHI, where the LBHI fills at least 98% ofthe through-pores and/or surface pores of the lithium-stuffed garnet,and where the LBHI may be a composition havingA·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X is a halide wherein 0.1≤A≤4,0.1≤B≤4, and 0≤C≤9.

In certain embodiments, provided herein is a composite having alithium-stuffed garnet and an LBHI, where the LBHI fills at least 99% ofthe through-pores and/or surface pores of the lithium-stuffed garnet,and where the LBHI may be a composition havingA·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X is a halide wherein 0.1≤A≤4,0.1≤B≤4, and 0≤C≤9.

In certain embodiments, provided herein is a composition having an LBHIcoating on a roughened lithium-stuffed garnet where the LBHI may be acomposition having A·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X is a halidewherein 0.1≤A≤4, 0.1≤B≤4, and 0≤C≤9.

In certain embodiments, provided herein is a composition having an LBHIon a curved lithium-stuffed garnet where the LBHI may be a compositionhaving A·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X is a halide wherein0.1≤A≤4, 0.1≤B≤4, and 0≤C≤9.

In certain embodiments, provided herein is a composition having an LBHIcoating on a corrugated lithium-stuffed garnet where the LBHI may be acomposition having A·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X is a halidewherein 0.1≤A≤4, 0.1≤B≤4, and 0≤C≤9.

In certain embodiments, provided herein is a composition having an LBHIinterdigitated within a lithium-stuffed garnet where the LBHI may be acomposition having A·(LiBH₄)·B·(LiX)·C·(LiNH₂) wherein X is a halidewherein 0.1≤A≤4, 0.1≤B≤4, and 0≤C≤9.

In certain embodiments, provided herein is a method for coating alithium ion conducting separator electrolyte, the method including: a)providing the separator electrolyte; and b) pressing a composition ofA·(LiBH₄)·B·(LiX)·C·(LiNH₂), where X may be fluorine, bromine, chlorine,iodine, or a combination thereof, and wherein 0.1≤A≤3, 0.1≤B≤4, and0≤C≤9 at a temperature between 100-280° C. at a pressure of 10-2000 PSIon at least one surface of the separator. For example, in oneembodiment, the method for coating a lithium ion conducting separatorelectrolyte includes a) providing the separator electrolyte; and b)pressing a composition of A·(LiBH₄)·B·(LiX)·C·(LiNH₂), where X isfluorine, and wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 at a temperaturebetween 100-280° C. at a pressure of 10-2000 PSI on at least one surfaceof the separator. By way of further example, in one embodiment, themethod for coating a lithium ion conducting separator electrolyteincludes a) providing the separator electrolyte; and b) pressing acomposition of A·(LiBH₄)·B·(LiX)·C·(LiNH₂), where X is bromine, andwherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 at a temperature between 100-280° C.at a pressure of 10-2000 PSI on at least one surface of the separator.By way of further example, in one embodiment, the method for coating alithium ion conducting separator electrolyte includes a) providing theseparator electrolyte; and b) pressing a composition ofA·(LiBH₄)·B·(LiX)C·(LiNH₂), where X is chlorine, and wherein 0.1≤A≤3,0.1≤B≤4, and 0≤C≤9 at a temperature between 100-280° C. at a pressure of10-2000 PSI on at least one surface of the separator. By way of furtherexample, in one embodiment, the method for coating a lithium ionconducting separator electrolyte includes a) providing the separatorelectrolyte; and b) pressing a composition ofA·(LiBH₄)·B·(LiX)·C·(LiNH₂), where X is iodine, and wherein 0.1≤A≤3,0.1≤B≤4, and 0≤C≤9 at a temperature between 100-280° C. at a pressure of10-2000 PSI on at least one surface of the separator. By way of furtherexample, in one embodiment, the method for coating a lithium ionconducting separator electrolyte includes a) providing the separatorelectrolyte; and b) pressing a composition of A·(LiBH₄)·B·(LiX)C(LiNH₂), where X is fluorine, bromine, and chlorine, and wherein0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 at a temperature between 100-280° C. at apressure of 10-2000 PSI on at least one surface of the separator. By wayof further example, in one embodiment, the method for coating a lithiumion conducting separator electrolyte includes a) providing the separatorelectrolyte; and b) pressing a composition ofA·(LiBH₄)·B·(LiX)·C(LiNH₂), where X is fluorine, bromine, and iodine,and wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 at a temperature between100-280° C. at a pressure of 10-2000 PSI on at least one surface of theseparator. By way of further example, in one embodiment, the method forcoating a lithium ion conducting separator electrolyte includes a)providing the separator electrolyte; and b) pressing a composition ofA·(LiBH₄)·B·(LiX)·C·(LiNH₂), where X is fluorine, chlorine, and iodine,and wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 at a temperature between100-280° C. at a pressure of 10-2000 PSI on at least one surface of theseparator. By way of further example, in one embodiment, the method forcoating a lithium ion conducting separator electrolyte includes a)providing the separator electrolyte; and b) pressing a composition ofA·(LiBH₄)·B·(LiX)·C·(LiNH₂), where X is bromine, chlorine, and iodine,and wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 at a temperature between100-280° C. at a pressure of 10-2000 PSI on at least one surface of theseparator.

In certain embodiments, provided herein is a method for coating alithium ion conducting separator electrolyte, the method including: a)providing the separator electrolyte; and b) pressing a composition ofA·(LiBH₄)·B·(LiX)·C·(LiNH₂), where X may be fluorine, bromine, chlorine,iodine, or a combination thereof, and wherein 0.1≤A≤3, 0.1≤B≤4, and0≤C≤9 at a temperature between 100-280° C. at a pressure of 10-2000 PSIon at least one surface of the separator. For example, in oneembodiment, the method for coating a lithium ion conducting separatorelectrolyte includes a) providing the separator electrolyte; and b)pressing a composition of A·(LiBH₄)·B·(LiX)·C·(LiNH₂), where X isfluorine, and wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 at a temperaturebetween 100-280° C. at a pressure of 10-2000 PSI on at least one surfaceof the separator. By way of further example, in one embodiment, themethod for coating a lithium ion conducting separator electrolyteincludes a) providing the separator electrolyte; and b) pressing acomposition of A·(LiBH₄)·B·(LiX)·C·(LiNH₂), where X is bromine, andwherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 at a temperature between 100-280° C.at a pressure of 10-2000 PSI on at least one surface of the separator.By way of further example, in one embodiment, the method for coating alithium ion conducting separator electrolyte includes a) providing theseparator electrolyte; and b) pressing a composition ofA·(LiBH₄)·B·(LiX)·C·(LiNH₂), where X is chlorine, and wherein 0.1≤A≤3,0.1≤B≤4, and 0≤C≤9 at a temperature between 100-280° C. at a pressure of10-2000 PSI on at least one surface of the separator. By way of furtherexample, in one embodiment, the method for coating a lithium ionconducting separator electrolyte includes a) providing the separatorelectrolyte; and b) pressing a composition ofA·(LiBH₄)·B·(LiX)·C·(LiNH₂), where X is iodine, and wherein 0.1≤A≤3,0.1≤B≤4, and 0≤C≤9 at a temperature between 100-280° C. at a pressure of10-2000 PSI on at least one surface of the separator. By way of furtherexample, in one embodiment, the method for coating a lithium ionconducting separator electrolyte includes a) providing the separatorelectrolyte; and b) pressing a composition ofA·(LiBH₄)·B·(LiX)·C·(LiNH₂), where X is fluorine, bromine, and chlorine,and wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 at a temperature between100-280° C. at a pressure of 10-2000 PSI on at least one surface of theseparator. By way of further example, in one embodiment, the method forcoating a lithium ion conducting separator electrolyte includes a)providing the separator electrolyte; and b) pressing a composition ofA.(LiBH₄)·B·(LiX)·C·(LiNH₂), where X is fluorine, bromine, or iodine,and wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 at a temperature between100-280° C. at a pressure of 10-2000 PSI on at least one surface of theseparator. By way of further example, in one embodiment, the method forcoating a lithium ion conducting separator electrolyte includes a)providing the separator electrolyte; and b) pressing a composition ofA·(LiBH₄)·B·(LiX)·C·(LiNH₂), where X is fluorine, chlorine, or iodine,and wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 at a temperature between100-280° C. at a pressure of 10-2000 PSI on at least one surface of theseparator. By way of further example, in one embodiment, the method forcoating a lithium ion conducting separator electrolyte includes a)providing the separator electrolyte; and b) pressing a composition ofA·(LiBH₄)·B·(LiX)·C·(LiNH₂), where X is bromine, chlorine, or iodine,and wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 at a temperature between100-280° C. at a pressure of 10-2000 PSI on at least one surface of theseparator.

In certain embodiments, the temperature in the method is below themelting point (T_(m)) of the separator, and is about 0.8 T_(m), whereT_(m) is expressed in Kelvin (K).

In certain embodiments, the method further includes c) holding thepressure between the composition and the separator for 1-300 min.

In certain embodiments, the method further includes d) cooling thecoated lithium ion conducting separator electrolyte under pressure for10-1000 min.

In certain embodiments, the method further includes d) cooling thecoated lithium ion conducting separator electrolyte under pressure for10-1000 min to room temperature.

In certain embodiments, provided is a method for coating a lithium ionconducting separator electrolyte, the method including a) providing alithium-stable separator electrolyte; b) providing a mixture of asolvent and an A·(LiBH₄)·B·(LiX)·C(LiNH₂) precursor; and c) depositingthe mixture on the separator by spray coating, spin coating, dipcoating, slot die coating, gravure coating, or microgravure coating. Forexample, in one embodiment, provided is a method for coating a lithiumion conducting separator electrolyte, the method including a) providinga lithium-stable separator electrolyte; b) providing a mixture of asolvent and an A·(LiBH₄)·B·(LiX)·C·(LiNH₂) precursor; and c) depositingthe mixture on the separator by spray coating. By way of furtherexample, in one embodiment, provided is a method for coating a lithiumion conducting separator electrolyte, the method including a) providinga lithium-stable separator electrolyte; b) providing a mixture of asolvent and an A·(LiBH₄)·B·(LiX)·C·(LiNH₂) precursor; and c) depositingthe mixture on the separator by spin coating. By way of further example,in one embodiment, provided is a method for coating a lithium ionconducting separator electrolyte, the method including a) providing alithium-stable separator electrolyte; b) providing a mixture of asolvent and an A·(LiBH₄)·B·(LiX)·C·(LiNH₂) precursor; and c) depositingthe mixture on the separator by dip coating. By way of further example,in one embodiment, provided is a method for coating a lithium ionconducting separator electrolyte, the method including a) providing alithium-stable separator electrolyte; b) providing a mixture of asolvent and an A·(LiBH₄)·B·(LiX)·C·(LiNH₂) precursor; and c) depositingthe mixture on the separator by slot die coating. By way of furtherexample, in one embodiment, provided is a method for coating a lithiumion conducting separator electrolyte, the method including a) providinga lithium-stable separator electrolyte; b) providing a mixture of asolvent and an A·(LiBH₄)·B·(LiX)·C·(LiNH₂) precursor; and c) depositingthe mixture on the separator by gravure coating. By way of furtherexample, in one embodiment, provided is a method for coating a lithiumion conducting separator electrolyte, the method including a) providinga lithium-stable separator electrolyte; b) providing a mixture of asolvent and an A·(LiBH₄)·B·(LiX)]C·(LiNH₂) precursor; and c) depositingthe mixture on the separator by microgravure coating.

In certain embodiments, the solvent in the method is selected from thegroup consisting of tetrahydrofuran, diethyl ether, methanol, andethanol. For example, in one embodiment, the solvent in the method istetrahydrofuran. By way of further example, in one embodiment, thesolvent in the method is diethyl ether. By way of further example, inone embodiment, the solvent in the method is ethanol. By way of furtherexample, in one embodiment, the solvent in the method is methanol.

In certain embodiments, the lithium-stable separator in the method hasdefects on the surface.

In certain embodiments, provided is a composition includingA·(LiBH₄)·B·(LiX)·C·(LiNH₂), where X is fluorine, bromine, chloride,iodine, or a combination thereof, and wherein 0.1≤A≤3, 0.1≤B≤4, and0≤C≤9 having a XRD pattern characterized by peaks at approximately14.5°, 15.5°, 16.4° 19.3° and 29.6° 2θ. For example, in one embodiment,provided is a composition including A.(LiBH₄).B.(LiX).C.(LiNH₂), where Xis fluorine, and wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 having a XRDpattern characterized by peaks at approximately 14.5°, 15.5°, 16.4°19.3° and 29.6° 2θ. By way of further example, in one embodiment,provided is a composition including A·(LiBH₄)·B·(LiX)·C·(LiNH₂), where Xis bromine, and wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 having a XRD patterncharacterized by peaks at approximately 14.5°, 15.5°, 16.4° 19.3° and29.6° 2θ. By way of further example, in one embodiment, provided is acomposition including A·(LiBH₄)·B·(LiX)·C·(LiNH₂), where X is chloride,and wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 having a XRD patterncharacterized by peaks at approximately 14.5°, 15.5°, 16.4° 19.3° and29.6° 2θ. By way of further example, in one embodiment, provided is acomposition including A—(LiBH₄)—B—(LiX)—C—(LiNH₂), where X is iodine,and wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 having a XRD patterncharacterized by peaks at approximately 14.5°, 15.5°, 16.4° 19.3° and29.6° 2θ. By way of further example, in one embodiment, provided is acomposition including A·(LiBH₄)·B·(LiX)·C·(LiNH₂), where X is fluorine,bromine, and chloride, and wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 having aXRD pattern characterized by peaks at approximately 14.5°, 15.5°, 16.4°19.3° and 29.6° 2θ. By way of further example, in one embodiment,provided is a composition including A·(LiBH₄)·B·(LiX)·C·(LiNH₂), where Xis fluorine, bromine, and iodine, and wherein 0.1≤A≤3, 0.1≤B≤4, and0≤C≤9 having a XRD pattern characterized by peaks at approximately14.5°, 15.5°, 16.4° 19.3° and 29.6° 2θ. By way of further example, inone embodiment, provided is a composition includingA·(LiBH₄)·B·(LiX)·C·(LiNH₂), where X is fluorine, chloride, and iodine,and wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 having a XRD patterncharacterized by peaks at approximately 14.5°, 15.5°, 16.4° 19.3° and29.6° 2θ. By way of further example, in one embodiment, provided is acomposition including A·(LiBH₄)·B·(LiX)·C·(LiNH₂), where X is bromine,chlorine, and iodine, and wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 having aXRD pattern characterized by peaks at approximately 14.5°, 15.5°, 16.4°19.3° and 29.6° 2θ.

EXAMPLES

In the examples described herein, the subscript values for thelithium-stuffed garnets represent elemental molar ratios of theprecursor chemicals used to make the claimed composition.

Electron microscopy was performed in a FEI Quanta SEM, a Helios 600i, ora Helios 660 FIB-SEM, though equivalent tools may be substituted. XRDwas performed in a Bruker D8 Advance ECO or a Rigaku Miniflex 2. EIS wasperformed with a Biologic VMP3, VSP, VSP300, SP150, or SP200.

Example 1 Garnet Coated with LBHI

A LBHI powder was prepared by mixing three (3) molar parts LiBH₄ withone (1) molar part LiI. The mixture was then subjected to two (2)millings in zirconia vessels at 300 rpm for 8 h, followed by annealingat 300° C. in a sealed vessel and cooled to room temperature to form amixed and annealed LBHI powder.

A thin garnet film (Li-stuffed garnet characterized as approximatelyLi_(7−x)La₃Zr₂O₁₂Al₂O₃) was prepared as follows. Garnet precursors weremixed in a molar ratio of 6-7:1.5:2:0.1-1.5 of LiOH, ZrO₂, La₂O₃, andboehmite. The mixed precursors were milled in a ball mill and calcinedat 700-1000° C. for 1-10 hours to form the cubic garnet phase withsecond phases. The powder was milled in a wet mill with solvent,surfactant, and dispersant. A binder solution was prepared by dissolvingbinder in the same solvent. The binder solution and powder slurry weremixed and tape cast on a mylar substrate with a doctor blade of gapheight 10-300 μm to form a cast green tape. The green tape was releasedfrom the substrate, cut to the desired size, sintered between setters at800-1200° C. for 1-10 hours and cooled to form a sintered garnet thinfilm.

Mixed and annealed LBHI powder (1-4 g) was heated to 300-350° C. underan argon atmosphere in a boron nitride or alumina crucible placed in astainless steel heating block equipped with a band heater for about 2 huntil the LBHI powder melted. The thin garnet film was dip-coated onceinto molten LBHI, at 300-350° C., under argon with a dwell time of 600s. The thin garnet film was then withdrawn from the molten LBHI at arate of 0.05-300 mm min⁻¹ and allowed to cool under argon for 5 s to 5min to provide a dip-coated LBHI garnet. Characteristics for thedip-coated LBHI garnet and the molten and stable LBHI are describedbelow with reference to one or more of the Figures.

FIG. 4 is a cross-section of a dip-coated LBHI-garnet, made by themethod in the previous paragraph. FIG. 4 shows surface channels,through-pores, or surface pores that pass into the garnet surface andthat are filled with LBHI. The channels, through-pores, or surface poresare present at least 100 μm below the garnet surface. For example, A andB in FIG. 4 indicate LBHI within one or more channels, through-pores, orsurface pores and defects in the garnet surface. FIG. 5 shows adip-coated LBHI-garnet, made by the method in the previous paragraph,where LBHI penetration extends at least 100 μm into the garnet surface.The iodine signal from the EDX is shown. Unexpectedly, the LBHI wets alithium-stuffed garnet surface sufficiently to wick into deep pores.

FIG. 8A shows an XRPD plot for a dip-coated LBHI-garnet (top) and areference spectra of LBHI (bottom) including characteristic peaks forLiI and LiBH₄. FIG. 8B shows another XRPD plot for a dip coated LBHIwith a wider 20 range including characteristic peaks at approximately14.5°, 15.5°, 16.4° 19.3° and 29.6° 2θ.

Example 2 Copper Coated with LBHI

LBHI was prepared and heated to 300-350° C., as in Example 1. A thincopper current collector foil was then dip-coated once into the moltenLBHI at 300-350° C. under argon with a dwell time of 600 s. The copperwas then withdrawn from the molten LBHI at a rate of 0.05-300 mm min⁻¹and allowed to cool under argon for 5 s to 5 min to provide a dip-coatedLBHI copper.

Example 3 ASR and Calendar Life

Dip-coated LBHI-garnet was prepared as in Example 1. ASR and calendarlife were tested as follows. Uncoated garnet and dip-coated LBHI garnetwere contacted on both sides with Li electrodes (8 mm contact area) andwere subjected to 0.5 mA cm² current density with 30 s pulses twicedaily (forward and reverse) at 80° C. and 300 PSI. FIG. 7 shows that,unexpectedly, uncoated garnet (gray line, A) had comparatively highermagnitudes of ASR than dip-coated LBHI garnet (black line, B). Further,the ASR was stable over time (i.e., non-increasing), which is adesirable feature for batteries.

Example 4 Cycling

Separators (uncoated garnet films or LBHI-coated garnet films preparedaccording to Example 1) were placed in a symmetric electrochemical cellwith Li-metal electrodes on both sides of the samples. FIG. 11 shows thetesting apparatus used. 5000 PSI of hydrostatic pressure was uniaxiallyapplied to both sides of the cells under controlled temperature andunder argon. Then, 5 cycles of 20 planar microns of lithium(approximately 4 mAh/cm²) at 2 mA/cm² at 80° C. were passed over an 8 mmelectrode contact area. For surviving (non-shorted samples), the currentwas increased to 3 mAh/cm² at 80° C. For surviving samples, the currentwas then increased to 4 mAh/cm² at 80° C. followed by increasing to 5mAh/cm² at 80° C. for surviving samples. FIG. 6 shows a survivabilityplot as a function of current density of uncoated garnet (dotted grayline) with garnet dip-coated with LBHI (solid black line) wheredip-coated LBHI garnet had improved survivability as compared to theuncoated garnet at higher current density. The larger surviving fractionof LBHI-coated separators at high current density shows that theLBHI-coated separators were more robust to dendrite formation than theuncoated garnet separators.

Example 5 DSC

Differential scanning calorimetry (DSC) experiments for LBHI powder withvarying amounts of amide dopants and LiI, were conducted.

A LBHI powder with varying amounts of amide dopants and LiI was preparedaccording to the methods in Example 1. LiBH₄ and LiI were mixed atdetermined ratios. The mixture was then subjected to two (2) millings inzirconia vessels at 300 rpm for 8 h, followed by annealing at 300° C.The resulting powder (1-4 g) was heated to 300-350° C. under an argonatmosphere in a boron nitride or alumina crucible placed in a stainlesssteel heating block equipped with a band heater for about 2 h until thepowder melted.

The introduction of amides allowed for the formation of, in someexamples, a eutectic mixture where the melting temperature for the LBHImay be reduced (or modified) depending on the amide content. Forexample, LiNH₂:LiBH₄:LiI (3:3:2) provided a melting point of about 120°C. with an dip-coating temperature range of about 120-165° C. In anotherexample, LiNH₂:LiBH₄:LiI (9:3:4) provided a melting point of about 125°C. with a dip coating temperature range of about 125-160° C. In anotherexample, LiNH₂:LiBH₄:LiI (9:3:2) provided a phase transition at about85° C., and a melting point of about 125° C. Gas evolution at about 100°C. was observed for LiNH₂:LiBH₄:LiI (9:3:2).

The separator material, LBHClN—LiNH₂:LiBH₄:LiCl (3:3:2)—orLBHIN—LiNH₂:LiBH₄:LiI (3:3:2)—was dip-coated onto a metal foil substratethat served as a back electrode. After cooling, a metal foil was placedon top to serve as a top electrode. Both electrodes were blocking tolithium. EIS was performed on the cell between 0.1 Hz 100 kHz and thetotal resistance was extracted. The total resistance represents the bulkresistance of LBHClN or LBHIN, from which conductivity may becalculated. The results are shown in FIG. 17.

Example 6 Total Resistance

LBHI was prepared, and garnet was coated with LBHI as in Example 1. FIG.9 shows an Arrhenius plot of conductance (1/R, where resistance ismeasured in ohms) versus reciprocal temperature (1000/T) (T in Kelvin),where an LBHI coated lithium-stuffed garnet reduced the surfaceresistance of the lithium-stuffed garnet. As shown in FIG. 9, the LBHIcoated garnet (top plot) had a more shallow slope compared to non-coatedgarnet (bottom plot), indicative of a lower activation energy and lowerarea-specific surface resistance. Alternatively stated, the LBHI coatedsubstrate reduced the surface resistance of the lithium-stuffed garnet.

Example 7 Conductivity Following Amide Doping

LBHI was prepared, and samples of 3 compositions of LiNH₂:LiBH₄:LiI wereprepared for comparison. Each powder was compacted in a die under apressure of 100-10,000 PSI to form a pressed pellet. After applyingmetallic electrodes, Electrochemical Impedance Spectroscopy (EIS) wasperformed on the pressed pellets to measure the bulk conductivity ofeach sample prepared by the method in this Example. EIS was performed byattaching a Biologic VMP3 to lithium contacts deposited on two sides ofa sample. An AC voltage of 25 mV rms is applied and swept across afrequency of 300 kHz0.1 mHz while the current is measured. As is knownin the art, EIS allows partitioning of the ASR into bulk and interfacialASR by resolving two semicircles in a Nyquist plot. An interfacial ASR(ASR_(interface)) is calculated from the interfacial resistance(R_(interface)) via the equation, ASR_(interface)=R_(interface)*A/2where A is the area of the electrodes in contact with the separator andthe factor of 2 accounts for 2 interfaces, assuming they are symmetric.Ionic conductivity, σ_(i), is calculated from the bulk resistance(R_(bulk)) via σ_(i)=d/R_(bulk)A where d is the thickness of the sample.The results of a conductivity measurement are shown in FIG. 10. Notably,LiNH₂:LiBH₄:LiI (9:3:4) shows a 10-fold increase in conductivity at 60°C. versus LiBH₄:LiI (3:1).

Example 8 Full Cell with LBHClN Bonding Lithium-Stuffed Garnet Film andSolid-State Cathode (SSC)

LBHClN was prepared by mixing three (3) molar parts LiBH₄, three (3)molar parts of LiNH₂, with one (1) molar part LiCl. The mixture was thensubjected to two (2) millings in zirconia vessels at 300 rpm for 8 h,followed by annealing in a sealed vessel at 180° C. for 2 hours andcooling to form a LBHClN powder.

Lithium-stuffed garnet film was prepared as in Example 1 and lithiummetal was applied on one side. Then the LBHClN powder was dropped on theother side of the lithium-stuffed garnet film. The lithium-stuffedgarnet with LBHClN powder on it was then heated to 80-140° C. at whichpoint the LBHClN powder melted.

A Sulfide containing solid-state cathode film (SSC) was prepared. TheSSC included a sulfide catholyte, LSTPS, and cathode active materials(NCA) with a LSTPS:NCA volumetric ratio of approximately ⅓ and ⅔. Asmall amount of carbon and binder, about 0-5 wt %, was added to theLSTPS and NCA. These resulting combination of LSTPS/NCA/carbon/binderwas suspended in toluene at a mass loading of 20% powder in toluene.Then the suspension was mixed using a Flacktek and Filmix for 15 minsand 6 mins, respectively. The mixture then was casted on tocarbon-coated aluminum foil and allowed to dry in an argon atmosphereuntil toluene evaporated. The film was punched to the desired size. TheSSC film was densified at 180° C. under pressure of 300,000 PSI. Thiscathode is labeled A in FIG. 14. A bonding layer LBHClN (labeled B inFIG. 14) was cast on top of the cathode. A thin film lithium-stuffedgarnet separator was pressed on the bonding layer. The thin filmlithium-stuffed garnet separator is labeled C in FIG. 13.

Then the SSC film was placed on top of the melted LBHClN powder. The SSCfilm was then pressed at 10-2000 pounds per square inch (PSI) whilebeing cooled to room temperature. This resulted in a full cell as shownin FIG. 13. The cell was cycled at C/10 rate, at 45° C. The cycling dataand full cell ASR are shown in FIGS. 15 and 16, respectively.

Example 9 Spin Casting

An LBHXN powder was fabricated as above, where X was be Cl, Br, or I, ora mixture thereof. Spin casting was used to deposit the bonding layer ofLBHXN thin film on to a lithium-stuffed garnet or on to a SSC film. Inthis procedure, a small amount of LBHXN powder was applied to the centerof the lithium-stuffed garnet or SSC film, which was on a chuck of aspin coater heated to the LBHXN melting temperature (−100-280° C.).LBHXN melted once the melting temperature was reached. A flat spatulawas used to cast the melted LBHXN on the substrate to cover the area.The spin coater was turned on to the speed of 100 rpm to 5000 rpm whilethe chuck was still at the temperature needed to melt LBHXN. The spincoater was turned off after 1-10 min. After cooling to room temperature,a uniform coating of LBHXN was achieved on the substrate.

Example 10 LBHIN Composition

LBHIN having the composition LiNH₂:LiBH₄:LiI (3:3:2) was coated on asolid-state cathode film by the drop casting method. Specifically, LBHINpowder was prepared and cast on a densified solid-state cathode. Anuncoated lithium-stuffed film (made according to Example 1) was pressedon the LBHIN layer at 20-2000 PSI and 20-350° C.

In FIG. 12, A is the solid-state cathode film and B is the LBHIN.

Although the foregoing embodiments have been described in some detailfor purposes of clarity of understanding, it will be apparent thatcertain changes and modifications may be practiced within the scope ofthe appended claims. It should be noted that there are many alternativeways of implementing the processes, systems and apparatus of the presentembodiments. Accordingly, the present embodiments are to be consideredas illustrative and not restrictive, and the embodiments are not to belimited to the details given herein.

What is claimed is:
 1. A substrate comprising a first layer, wherein thefirst layer comprises: A·(LiBH₄)·B·(LiX)·C·(LiNH₂), wherein X isfluorine, bromine, chlorine, or iodine, and wherein 2.5<A<3.5,1.5<B<2.5, and 2.5<C<3.5.
 2. The substrate of claim 1, wherein X ischlorine.
 3. The substrate of claim 1, wherein X is bromine.
 4. Thesubstrate of claim 1, wherein X is iodine.
 5. The substrate of claim 2,wherein the first layer is 3LiBH₄·2LiCl·3LiNH₂ or 3LiBH₄·4LiCl·9LiNH₂.6. The substrate of claim 3, wherein the first layer is3LiBH₄·2LiBr·3LiNH₂ or 3LiBH₄·4LiBr·9LiNH₂.
 7. The substrate of claim 4,wherein the first layer is 3LiBH₄·2LiI·3LiNH₂ or 3LiBH₄·4LiI·9LiNH₂. 8.The substrate of claim 1, further comprising a second layer, wherein thesecond layer comprises an oxide, a sulfide, a sulfide-halide, or acombination thereof.
 9. The substrate of claim 8, wherein the secondlayer comprises a sulfide or sulfide-halide selected from LSS, SLOPS,LSTPS, SLOBS, LATS, or LPS+X, wherein X is selected from the groupconsisting of Cl, I, and Br.
 10. The substrate of claim 9 wherein theLPS+X is LPSI.
 11. The substrate of claim 8, wherein the sulfide is alithium sulfide characterized by one of the following formula:Li_(a)Si_(b)Sn_(c)P_(d)S_(e)O_(f), wherein 2≤a≤8, 0≤b≤1, 0≤c≤1, b+c=1,0.5≤d≤2.5, 4≤e≤12, and 0<f≤10; Li_(a)Si_(b)P_(c)S_(d)X_(e), wherein8<a<12, 1<b<3, 1<c<3, 8<d<14, and 0<e<1, wherein X is F, Cl, Br, or I;Li_(g)As_(h)Sn_(j)S_(k)O_(l), wherein 2≤g≤6, 0≤h≤1, 0≤j≤1, 2≤k≤6, and0≤l≤10; Li_(m)P_(n)S_(p)I_(q), wherein 2≤m≤6, 0≤n≤1, 0≤p≤1, 2≤q≤6; amixture of (Li₂S):(P₂S₅) having a molar ratio of Li₂S:P₂S₅ from about10:1 to about 6:4 and LiI, wherein the ratio of [(Li₂S):(P₂S₅)]:LiI isfrom 95:5 to 50:50; LPS+X, wherein X is selected from Cl, I, or Br;vLi₂S+wP₂S₅+yLiX; vLi₂S+wSiS₂+yLiX; or vLi₂S+wB₂S₃+yLiX.
 12. Thesubstrate of claim 8, wherein the composition comprises: a mixture ofLiI and Al₂O₃; Li₃N; a mixture of LiBH₄ and LiX wherein X is selectedfrom Cl, I, or Br; or vLiBH₄+wLiX+yLiNH₂, wherein X is selected from Cl,I, or Br; and wherein coefficients v, w, and y are rational numbers from0 to
 1. 13. The substrate of claim 8, wherein the oxide is alithium-stuffed garnet oxide characterized by the formulaLi_(u)La_(y)Zr_(x)O_(y)·zAl₂O₃, wherein u is a rational number from 4 to8; v is a rational number from 2 to 4; x is a rational number from 1 to3; y is a rational number from 10 to 14; z is a rational number from0.05 to 1; and wherein u, v, x, y, and z are selected so that thelithium-stuffed garnet oxide is charge neutral.
 14. The substrate ofclaim 8, wherein the oxide is a lithium-stuffed garnet oxidecharacterized by the formula Li_(u)La_(v)Zr_(x)O_(y)·zTa₂O₅, wherein uis a rational number from 4 to 10; v is a rational number from 2 to 4; xis a rational number from 1 to 3; y is a rational number from 10 to 14;and z is a rational number from 0 to 1; wherein u, v, x, y, and z areselected so that the lithium-stuffed garnet oxide is charge neutral. 15.The substrate of claim 8, wherein the oxide is a lithium-stuffed garnetoxide characterized by the formula Li_(u)La_(v)Zr_(x)O_(y)·zNb₂O₅,wherein u is a rational number from 4 to 10; v is a rational number from2 to 4; x is a rational number from 1 to 3; y is a rational number from10 to 14; and z is a rational number from 0 to 1; wherein u, v, x, y,and z are selected so that the lithium-stuffed garnet oxide is chargeneutral.
 16. The substrate of claim 8, wherein the oxide is alithium-stuffed garnet oxide characterized by the formulaLi_(u)La_(v)Zr_(x)O_(y)·zGa₂O₃, wherein u is a rational number from 4 to10; v is a rational number from 2 to 4; x is a rational number from 1 to3; y is a rational number from 10 to 14; and z is a rational number from0 to 1; wherein u, v, x, y, and z are selected so that thelithium-stuffed garnet oxide is charge neutral.
 17. The substrate ofclaim 1, wherein the substrate is a thin film and wherein the thin filmhas a porosity less than 5 percent.
 18. The substrate of claim 1,wherein the substrate has grains with a d₉₀ grain size of less than 10μm.
 19. The substrate of claim 1, wherein the substrate has a lithiumion conductivity greater than 1×10⁻⁴S/cm at 60° C.
 20. A method formaking a thin film comprising the substrate of claim 1, comprising: (a)providing a powder mixture, wherein the mixture comprises:A·(LiBH₄)·B·(LiX)·C·(LiNH₂); wherein X is F, Br, Cl, or I; and wherein2.5<A<3.5, 1.5<B<2.5, and 2.5<C<3.5; (b) dropping, casting, or sprayingthe powder mixture on a substrate; (c) heating the powder mixture withsubstrate to the mixture melting point but lower than the powder mixturedecomposition temperature; and (d) cooling the substrate to roomtemperature.